JP3455023B2 - Method for producing olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an olefin polymer.
And a method for producing the same. For more information,
The density of the olefin polymer, especially the propylene polymer, is 0.90
Stereoregular polymer in the range of 0 to 0.906 g / ml
Method for producing a polymer with a small amount of fine powder in a high yield
It is about. [0002] 2. Description of the Related Art Magnesium, titanium, electron donating compounds
Products, solid catalyst components containing halogen, organic aluminum
And a third component such as a silicon compound and a silicon compound.
A method for producing an olefin polymer using a catalyst
Many proposals have been made and are well known. For example, Japanese Patent Application Laid-Open No. 62-18406 discloses
Is a solid formed by polymerizing 0.1 g or more of olefin
Catalyst components, organoaluminum compounds and certain organic
The use of a specific catalyst consisting of a combination of iodine compounds
A method for producing an olefin polymer is disclosed. In Japanese Patent Application Laid-Open No. 2-84404,
Contains magnesium, titanium and halogen as essential components
Titanium catalyst component contained as an organic aluminum
Compounds and cyclopentyl, cycloentenyl,
Organic containing clopentadienyl group or derivatives thereof
Existence of catalyst for olefin polymerization formed from silicon compounds
There is disclosed a method for polymerizing olefins.
It is also noted that pre-polymerization is performed before performing such polymerization.
It is listed. By the way, each of the above prior arts is
When used as a catalyst for polymerization of
So-called deashing process to remove catalyst residues such as chlorine and titanium
Starting with the development of a catalyst component that is so active that it can be omitted,
In addition, the improvement of the stereoregular polymer yield and the polymerization during polymerization
The focus is on increasing the sustainability of the activity.
Each of them has achieved excellent results. In the presence of a highly active type catalyst as described above
Olefins, especially propylene
In the case of polymerization, the conventional titanium trichloride type solid catalyst
Component and organoaluminum compound and the third component
Compared to using a catalyst formed from a child-donating compound
As a result, the yield of the produced polymer is high, and
It has good rules, but its density is higher than 0.906g / ml
Film and sheet
When processing at high speed, it breaks during high-speed molding
Troubles such as loss of transparency will occur
There was a problem. As a means for solving such a problem, the above high
Active type catalysts are olefins, especially propylene
Lower the polymerization temperature or use a small amount of
Attempted methods such as coexisting styrene with comonomer
Control the density of the resulting polymer to some extent.
Rolling is possible, but in the case of the slurry method,
Low molecular weight polymers soluble in co-solvents,
Attack poly with extremely low stereoregularity
Propylene generation rate (hereinafter abbreviated as "attack generation rate")
You. ) Triggers an unwanted phenomenon of higher
You. [0008] Attack in the polymerization by the slurry method
When the production rate increases, the particles of the produced polymer are separated from the polymerization solvent.
After separation, an extraction step is required, and the reactor
And the cost of polymer production
There is a problem in stable operation, and more variety in one plant
Changes in operating conditions during continuous operation
In addition, it hinders the control of the products involved, and
It had an unfavorable effect on driving. Also, the polymerization
Fine powder in the body, especially with a particle size of less than 100 microns
Clogging of pipes in the polymerization process
Causes trouble in polymer separation and drying processes
In some cases, this was an issue for which improvement was desired. Accordingly, the present applicant has disclosed in Japanese Patent Application Laid-open No. Hei 8-3214.
In Japanese Patent Application Laid-Open No. 8-67711, the polymerization
And olefins by slurry method using solvent at the time
In other words, in the polymerization of propylene, a solid that is insoluble in the polymerization solvent
While maintaining a high recovery rate of the regular polymer,
Stereoscopic rules with body density in the range of 0.900 to 0.906 g / ml
Catalyst for Olefin Polymerization from which Conductive Polymers are Easily Obtained
Proposal of components and catalysts to solve the problems of the prior art
It has an excellent effect on solving. [0010] SUMMARY OF THE INVENTION
Polymerization of olefins, especially solid catalysts for olefin polymerization,
When propylene is polymerized, the heat of reaction
Degradation of the catalyst occurs, thereby reducing the catalyst activity,
Deterioration of the stereoregularity of the resulting polymer and the desired density
No polymer is obtained. In addition, the solid touch due to this heat of reaction
Due to the destruction of particles of the medium component, the resulting polymer contains a large amount of fine powder.
In rare cases, the particle size distribution also tends to broaden,
There is a problem that the bulk specific gravity is lowered. Fine polymer powder
As the number increases, uniform reaction may not be maintained
Sources of process failure such as blockage of piping at the time
And a broad particle size distribution results in a polymer
It has an unfavorable effect on the molding process. Also generate weight
Decrease in bulk specific gravity of coalescence directly leads to decrease in productivity
It is. The present invention is based on the prior art as described above.
Completed through various studies to solve the problems
The purpose is to polymerize olefins, especially propylene.
When used, the rate of attack generation is low and the density of the produced polymer is low.
A stereoregular polymer whose degree is in the range of 0.900 to 0.906 g / ml
A polymer that can be obtained in high yield and has few fine powders
To provide a method for producing an olefin polymer capable of producing
And there. [0012] Means for Solving the Problems To achieve the above object,
The method for producing an olefin polymer according to the present invention for (A)General formula Mg (OR ^Four ) _Two (Where R ^Four Is 1 carbon
To 4 alkyl groups or aryl groups. )
Alkoxymagnesium (a) represented by the following general formula I; Al (OR ^Five ) _m X _3-m (General formula I) (Where R ^Five Is an alkyl group having 1 to 4 carbon atoms or
1 or 2 alkyl groups having 1 to 3 carbon atoms
Is a substituted aralkyl group, and when m is 2 or more, R ^Five Is
Same or different, X represents a halogen element, m is 0 ≦ m
≦ 3. ) And the following general formula II: R ⁶ _n AlX _3-n (General formula II) (Where R ⁶ Is an alkyl group having 1 to 4 carbon atoms, X is hydrogen
Represents an atom or a halogen element, and n is 0 <n ≦ 3.
You. Select from aluminum compound group represented by)
At least one aluminum compound (b)
General formula Ti (OR ⁷ ) _p X _4-p (Where R ⁷ Is 1 carbon
X represents a halogen element, and p represents 0 to 4.
Or an integer from 1 to 3. Halogenated thi)
Tan compound (c), electron donating compound (d) and general
Formula R ⁸ _y Si (OR ⁹ ) _4-y (Where R ⁸ Is alkyl
Group, cycloalkyl group, phenyl group, vinyl group, allyl
Group or aralkyl group, which may be the same or different
No. R ⁹ Is an alkyl group having 1 to 4 carbon atoms, cycloalkyl
Group, phenyl group, vinyl group, allyl group, aralkyl group
May be the same or different. y is 0 or
It is an integer of 1 to 3. ) And the following general formula (where x is
Represents the average degree of polymerization, from 2 to 30,000, ^Ten
To R ¹⁷ Is mainly a methyl group, and sometimes R ^Ten To R
¹⁷ Is partly a phenyl group, hydrogen, higher fatty acid residue,
Substituted with a xy-containing group or a polyoxyalkylene group
And the compound of the above general formula is R ¹³ And R ¹⁴ But
Including those forming cyclic polysiloxanes
No. Selected from the group of organosilicon compounds represented by
At least one organosilicon compound (e) Embedded image Are brought into contact in suspension,Magnesium, titanium
, Electron donating compounds, aluminum and halogen
Including a solid catalyst component, (B) General formula R¹ _qAlY_3-q (Where R¹Is an alkyl group having 1 to 4 carbon atoms, and Y is water
Any of nitrogen, chlorine, bromine and iodine, and q is 0 <q
<3 is a real number. Organoalumination represented by)
Compound and (C) General formula R^Two _rSi (OR^Three)_4-r (Where R^TwoIs an alkyl group having 1 to 12 carbon atoms, cyclo
Alkyl group, phenyl group, vinyl group, allyl group, arral
It may be the same or different in any of the kill groups. R^ThreeIs
An alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
Any of a nyl group, vinyl group, allyl group, and aralkyl group
And may be the same or different. r is 0 or an integer from 1 to 3
Is a number. Contact consisting of an organosilicon compound represented by
There is one type in the polymerization method of olefins using a solvent.
Or two or more olefins per 1 g of solid catalyst component (A)
0.01 to 1.0 g in the presence of an inert hydrocarbon solvent
The organoaluminum compound (B) and the solid catalyst component
(A) and, per titanium atom in the solid catalyst component (A),
The organoaluminum compound (B) is added in an amount of 0.5 to 50 mol.
Contact and then the resulting polymerization per g of solid catalyst component (A)
One or two or more types so that the body weight is in the range of 1 to 20 g
The above olefin was preliminarily polymerized in the range of 0 to 40 ° C.
Thereafter, main polymerization is performed.[0013] [0014] BEST MODE FOR CARRYING OUT THE INVENTION Used in the preparation of the above component (A)
Alkoxy magnesium [hereinafter referred to as “component (a)”
Has the general formula Mg (OR^Four)_Two(Where R^FourIs
Represents an alkyl or aryl group having 1 to 4 carbon atoms
You. ). Specifically,
Simagnesium, diethoxymagnesium, di-n-pro
Poxymagnesium, di-iso-propoxymagnesium
, Di-n-butoxymagnesium, di-iso-butoxyma
Gnesium, diphenoxymagnesium, ethoxymeth
Xymagnesium, ethoxy-n-propoxymagnesium
, N-butoxyethoxy magnesium, iso-butoxy
One or two or more such as toxin magnesium
Of which, among others, diethoxymagnesium or
Is preferably di-n-propoxy magnesium.
You. Further, the dia used for preparing the component (A)
Lucoxy magnesium is granular or powdery.
The shape may be irregular or spherical
You. If spherical diethoxymagnesium is used,
Polymer powder with good particle shape and narrow particle size distribution
Is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved.
Improved due to fines contained in the resulting polymer powder
Troubles such as blockage that occur are eliminated. The above spherical diethoxymagnesium is
Not necessarily a true sphere, but an ellipse or potato
Is used. Specifically, the spherical shape of the particles
The degree is expressed by the ratio of the major axis diameter l to the minor axis diameter w, l / w,
3 or less, preferably from 1 to 2, more preferably
Or 1 to 1.5. In addition, the dialkoxy magnesium is
The average particle size is from 1 micron to 200 microns
Can. Preferably between 5 microns and 150 microns
is there. The above spherical diethoxymagnesium field
The average particle size is from 1 micron to 100 microns, preferably
Preferably, it is 5 to 50 microns, more preferably
Preferably it is between 10 and 40 microns. Also,
Regarding the particle size, there are few fine or coarse powders,
It is desirable to use a sharp cloth. concrete
Have less than 20% of particles less than 5 microns,
Or 10% or less. Particles of 100 microns or more
10% or less, preferably 5% or less. further
The particle size distribution is expressed as ln (D90 / D10) (here, D90
Is the particle size at 90% of the cumulative particle size, D10 is the cumulative particle size
Represents the particle size at 10%).
And preferably 2 or less. The above dialkoxymagnesium is a component (A)
Do not necessarily have to be used as starting materials in the preparation of
For example, when preparing component (A),
An aliphatic monohydric alcohol having a prime number of 1 to 4 is converted to a catalyst such as iodine.
May be used obtained by reacting in the presence of. (A) Aluminum used for the preparation of the component
The compound [hereinafter sometimes referred to as “component (b) component”]
Among the aluminum compounds represented by the general formulas I and II
At least one selected from the group consisting of: Al (OR^Five)_mX_3-m    (General formula I) (Where R^FiveIs an alkyl group having 1 to 4 carbon atoms or
1 or 2 alkyl groups having 1 to 3 carbon atoms
Is a substituted aralkyl group, and when m is 2 or more, R^FiveIs
Same or different, X represents a halogen element, m is 0 ≦ m
≦ 3. ) R⁶ _nAlX_3-n          (General formula II) (Where R⁶Is an alkyl group having 1 to 4 carbon atoms, X is hydrogen
Represents an atom or a halogen element, and n is 0 <n ≦ 3.
You. ) Aluminum compound represented by the general formula I
As aluminum trihalide, alkoxyal
Minium dihalide, dialkoxy aluminum halide
And trialkoxy aluminum,
Examples include aluminum trichloride, aluminum
Mutribromide, aluminum triiodide, di
Ethoxy aluminum chloride, di-iso-propoxy
Aluminum chloride, dibutoxy aluminum chloride
Ride, ethoxy aluminum dichloride, iso-pro
Poxyaluminum dichloride, butoxyaluminium
Mudichloride, trimethoxyaluminum, trieth
Aluminum aluminum, tripropoxy aluminum, bird
-iso- Aluminum propoxy, aluminum tributoxy
Aluminum, tri-iso-butoxyaluminum, etc.
Among them, a preferred substance is aluminum trichloride.
, Di-iso-propoxy aluminum chloride, iso-
Propoxy aluminum dichloride, triethoxy
Luminium, tri-iso-propoxy aluminum
You. Aluminum compound represented by the general formula II
As trialkyl aluminum, dialkyl high
Dried, dialkyl aluminum halide and alk
Aluminum dihalide.
Is triethyl aluminum, tri-iso-butyl alkyl
Minium, diethyl aluminum hydride, di-iso
-Butyl hydride, diethyl aluminum chloride
, Di-iso-butyl aluminum chloride, ethyl acetate
Luminium dichloride, propyl aluminum dichloride
Ride, ethyl aluminum sesquichloride, butyl
Aluminum sesquichloride, etc.
Among them, preferably, triethyl aluminum, diethyl
Aluminum chloride, ethyl aluminum dichlora
It is ethyl aluminum sesquichloride. As the above component (b), the above general formula I and
One or more selected from the group of compounds of general formula II
The above can be used. The component (b) is directly
Or with toluene or xylene
Like aromatic hydrocarbons or hexane or heptane
Dissolved and diluted in organic solvents such as
You may. The halo used for preparing the component (A) of the present invention
Titanium genide compound [hereinafter sometimes referred to as “component (c)”
] Has the general formula Ti (OR⁷)_pX_4-p(Where R⁷
Represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen element.
And p is 0 or an integer from 1 to 3. )
Titanium halide or alkoxy titanium halide
is there. Specifically, as titanium tetrahalide, Ti
Cl_Four, TiBr_Four, TiI_Four, Alkoxy titanium hara
Ti (OCH_Three) Cl_Three, Ti (OC_TwoH
_Five) Cl_Three, Ti (OC_ThreeH₇) Cl_Three, Ti (On-
C_FourH₉) Cl_Three, Ti (OCH_Three)_TwoCl_Two, Ti
(OC_TwoH_Five)_TwoCl_Two, Ti (OC_ThreeH₇)_TwoC
l_Two, Ti (On-C_FourH₉)_TwoCl_Two, Ti (OCH
_Three)_ThreeCl, Ti (OC_TwoH_Five)_ThreeCl, Ti (OC_Three
H₇)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl etc. are examples
Is done. Of these, titanium tetrahalide is preferred.
And particularly preferably TiCl_FourIt is. These above
One or more titanium compounds may be used.
Furthermore, these components (c) are
Such as aromatic hydrocarbons or hexane or heptane
Dissolve and dilute in organic solvents such as aliphatic hydrocarbons
May be. (A) Preparation of electron donating compound used for preparation of component
The compound [hereinafter sometimes referred to as “component (d)”]
, Ethers, esters, aldehydes, keto
, Amines, acid halides, nitriles, etc.
Of which aromatic carboxylic acid diesters
Is preferably used. As aromatic carboxylic acid diesters,
Is a phthalic acid having a linear or branched chain having 1 to 12 carbon atoms.
Diesters of alkyl are preferred. The diester ingredient
Examples include dimethyl phthalate and diethyl phthalate.
G, di-n-propyl phthalate, di-iso-prop
Ruphthalate, di-n-butyl phthalate, di-iso
-Butyl phthalate, ethyl methyl phthalate, butyl
Ethyl phthalate, methyl (iso-propyl) phthale
, Ethyl-n-propylphthalate, ethyl-n-
Butyl phthalate, di-n-pentyl phthalate, di-
iso-pentyl phthalate, dihexyl phthalate,
Di-n-heptyl phthalate, di-n-octyl phthalate
, Bis (2-methylhexyl) phthalate, bis
(2-ethylhexyl) phthalate, di-n-nonylph
Tallate, di-isodecyl phthalate, bis (2,2
-Dimethylheptyl) phthalate, n-butyl (iso
-Hexyl) phthalate, ethyl (iso-octyl)
Phthalate, n-butyl (iso-octyl) phthalate
G, n-pentylhexyl phthalate, n-pentyl
(Iso-hexyl) phthalate, iso-pentyl
(Heptyl) phthalate, n-pentyl (iso-octyl)
Tyl) phthalate, n-pentyl (iso-nonyl) phenyl
Talate, iso-pentyl (n-decyl) phthale
G, n-pentyl (undecyl) phthalate, iso-
Pentyl (iso-hexyl) phthalate, n-hexyl
(Iso-octyl) phthalate, n-hexyl (i
so-nonyl) phthalate, n-hexyl (n-decyl)
F) phthalate, n-heptyl (iso-octyl) phenyl
Talate, n-heptyl (iso-nonyl) phthale
G, n-heptyl (neo-decyl) phthalate, is
An example is o-octyl (iso-nonyl) phthalate.
And one or more of these are used. this
Among them, diethyl phthalate, di-n-butyl phthalate
Or di-iso-butyl phthalate or bis (2
-Ethylhexyl) phthalate is preferably used. The above component (d) may be used alone or in combination of two or more.
If there are, there are no particular restrictions on the combination,
If acid diester is used, one phthalic diester
The total carbon number of the two alkyl groups of
The difference in the total carbon number of the two alkyl groups of the ester is 4 or more
It is preferable to select and combine them as follows. That
A specific example of the combination is as follows. (1) diethyl phthalate and di-n-butyl phthalate (2) Diethyl phthalate and di-iso-butyl phthalate
G (3) Diethyl phthalate and di-n-octyl phthalate (4) Diethyl phthalate and bis (2-ethylhexyl)
Phthalate (5) di-n-butyl phthalate and di-n-octyl phthalate
rate (6) Di-n-butyl phthalate and bis (2-ethylhexyl)
Sill) phthalate (7) diethyl phthalate and di-n-butyl phthalate
Bis (2-ethylhexyl) phthalate (8) Diethyl phthalate and di-iso-butyl phthalate
And bis (2-ethylhexyl) phthalate (A) Organosiliconization used for the preparation of the component
The compound [hereinafter sometimes referred to as “component (e)”] has the general formula
  R⁸ _ySi (OR⁹)_4-y(Where R⁸Is alkyl
Group, cycloalkyl group, phenyl group, vinyl group, allyl
Group or aralkyl group, which may be the same or different
No. R⁹Is an alkyl group having 1 to 4 carbon atoms, cycloalkyl
Group, phenyl group, vinyl group, allyl group, aralkyl group
May be the same or different. y is 0 or
It is an integer of 1 to 3. Phenylalkoxy represented by)
Sisilane, alkylalkoxysilane, phenylalkyl
Alkoxysilane, cycloalkylalkoxysila
, Cycloalkylalkylalkoxysilane or
Lucoxysilane. Specific examples of the above component (e) include
Methylmethoxysilane, trimethylethoxysilane,
L-n-propylmethoxysilane, tri-n-propyl
Ethoxysilane, tri-n-butylmethoxysilane,
L-iso-butylmethoxysilane, tri-t-butyl
Methoxysilane, tri-n-butylethoxysilane,
Licyclohexylmethoxysilane, tricyclohexyl
Ethoxysilane, dimethyldimethoxysilane, dimethyl
Diethoxysilane, di-n-propyldimethoxysila
, Di-iso-propyldimethoxysilane, di-n-
Propyldiethoxysilane, di-iso-propyldie
Toxysilane, di-n-butyldimethoxysilane, di-
iso-butyldimethoxysilane, di-t-butyldimene
Toxisilane, di-n-butyldiethoxysilane, n-
Butylmethyldimethoxysilane, bis (2-ethylhexyl)
Sil) dimethoxysilane, bis (2-ethylhexyl)
Diethoxysilane, dicyclohexyldimethoxysila
, Dicyclohexyldiethoxysilane, dicyclopen
Tyldimethoxysilane, dicyclopentyldiethoxy
Orchid, cyclohexylmethyldimethoxysilane, cyclo
Hexylmethyldiethoxysilane, cyclohexylethyl
Rudimethoxysilane, cyclohexyl (iso-propyl
Le) dimethoxysilane, cyclohexylethyldiethoxy
Silane, cyclopentylmethyldimethoxysilane, silane
Clopentylmethyldiethoxysilane, cyclopentyl
Ethyldiethoxysilane, cyclopentyl (iso-propyl)
Ropyl) dimethoxysilane, cyclohexyl (n-pen
Tyl) dimethoxysilane, cyclohexyl (n-
Le) diethoxysilane, cyclopentyl (iso-butyl)
L) dimethoxysilane, cyclohexyl (n-propyl
L) dimethoxysilane, cyclohexyl (n-propyl
Le) diethoxysilane, cyclohexyl (iso-pro
Pill) diethoxysilane, cyclohexyl (n-butyl)
Le) dimethoxysilane, cyclohexyl (n-butyl)
Diethoxysilane, cyclohexyl (iso-butyl)
Dimethoxysilane, diphenyldimethoxysilane, diph
Phenyldiethoxysilane, phenylmethyldimethoxy
Orchid, phenylmethyldiethoxysilane, phenylethyl
Rudimethoxysilane, phenylethyldiethoxysila
, Cyclohexyldimethylmethoxysilane, cyclohexane
Xyldimethylethoxysilane, cyclohexyldiethyl
Methoxysilane, cyclohexyldiethylethoxy
Orchid, 2-ethylhexyltrimethoxysilane, 2-d
Tylhexyltriethoxysilane, methyltrimethoxy
Silane, methyltriethoxysilane, ethyltrimethoxy
Sisilane, ethyltriethoxysilane, n-propyl
Limethoxysilane, n-propyltriethoxysilane,
iso-propyltrimethoxysilane, iso-propyl
Lutriethoxysilane, n-butyltrimethoxysila
, Iso-butyltrimethoxysilane, t-butyl
Limethoxysilane, n-butyltriethoxysilane,
Clohexyltrimethoxysilane, cyclohexyltri
Ethoxysilane, cyclopentyltrimethoxysilane,
Cyclopentyltriethoxysilane, vinyltrimethoxy
Sisilane, vinyltriethoxysilane, 2-ethylhexyl
Siltrimethoxysilane, 2-ethylhexyltriet
Xysilane, phenyltrimethoxysilane, phenylt
Liethoxysilane, tetramethoxysilane, tetraeth
Xysilane, cyclohexylcyclopentyldimethoxy
Silane, cyclohexylcyclopentyldiethoxysila
, Cyclohexylcyclopentyldipropoxysila
3-Methylcyclohexylcyclopentyl dimethoxy
Sisilane, 4-methylcyclohexylcyclopentyldi
Methoxysilane, 3,5-dimethylcyclohexylcycl
Lopentyl dimethoxysilane, 3-methylcyclohexyl
Rucyclohexyldimethoxysilane, bis (3-methyl
Cyclohexyl) dimethoxysilane, 4-methylcyclo
Hexylcyclohexyldimethoxysilane, bis (4-
Methylcyclohexyl) dimethoxysilane, 3,5 di
Methoxycyclohexylcyclohexyldimethoxysila
Bis (3,5-dimethylcyclohexyl) dimethoxy
Sisilane, tetramethoxysilane, tetraethoxysila
, Tetrapropoxysilane, tetrabutoxysilane, etc.
It is. Among the above, di-iso-propyldimethyl
Toxisilane, di-iso-butyldimethoxysilane,
Di-t-butyldimethoxysilane, dicyclohexyldi
Methoxysilane, dicyclohexyldiethoxysilane,
Cyclohexylmethyldimethoxysilane, dicyclopen
Tyldimethoxysilane, cyclopentylmethyldimethoxy
Sisilane, cyclohexylcyclopentyldimethoxysi
Run, 3-methylcyclohexylcyclopentyl dimeth
Xysilane, 4-methylcyclohexylcyclopentyl
Dimethoxysilane, 3,5-dimethylcyclohexyl
Clopentyldimethoxysilane, phenyltriethoxy
Silane, tetramethoxysilane, tetraethoxysila
Is preferably used, and the component (e) is
Two or more kinds can be used in combination. In addition to the above, the organosilicon compound of component (e)
Alternatively, a polysiloxane can be used. As polysiloxane
ThefollowingA general formula (wherein x represents an average degree of polymerization and 2
From 30,000 to R^TenTo R¹⁷Is methyl
And sometimes R^TenTo R¹⁷Is part of phenyl
Group, hydrogen, higher fatty acid residue, epoxy-containing group, polyoxy
Those substituted with a silalkylene group, and
The compound of formula R¹³And R¹⁴Is a cyclic polysiloxane with a methyl group
Including those forming sun. ) Policy
One of loxanes (hereinafter sometimes referred to as component (e)) or
Are two or more. [0034]Embedded image The polysiloxane is combined with silicone oil
Are generally referred to as having a viscosity of 2 to 10,000 centistokes at 25 ° C.
, Preferably 2 to 1,000 centistokes,
More preferably, having a density of 3 to 500 centistokes
Liquid, viscous, chain-like, partially hydrogenated, cyclic at temperature
Or modified polysiloxane. As the linear polysiloxane, dimethylpolysiloxane is used.
Polysiloxane, methylphenylpolysiloxane
As a hydrogenated polysiloxane, a hydrogenation rate of 10 to 80%
Methyl hydrogen polysiloxane is
Hexamethylcyclotrisiloxane,
Kutamethylcyclotetrasiloxane, decamethylcyclo
Pentasiloxane, 2,4,6-trimethylcyclotri
Siloxane, 2,4,6,8-tetramethylcyclotet
Lasiloxane and modified polysiloxane
Lower fatty acid group substituted dimethyl siloxane, epoxy group substituted di
Methylsiloxane, polyoxyalkylene-substituted dimethyl
Siloxane. Specific examples of each polysiloxane include commercial products
Name TSF 400, TSF 401, TSF 404, TSF 405,
TSF 4045, TSF 410, TSF 411, TSF 433,
TSF437, TSF 4420, TSF 451-5A, TSF 4
51-10A, TSF 451-50A, TSF 451-10
0, TSF 483, TSF 484
KF96, KF96L, KF96H, KF6
9, KF92, KF961, KF965, KF56, KF99, KF
94, KF995, KF105, KF351, HIVAC-F4, HIV
AC-F 5 (all products manufactured by Shin-Etsu Chemical Co., Ltd.)
You. One or more of the above polysiloxanes
By subjecting to a reaction in combination with other components (a) to (d),
High activity, while maintaining a predetermined polymer density, fine powder content
Solid catalyst component that can produce polymers with extremely low
It is done. These polysiloxanes are also
Organic solvents such as xylene, xylene, hexane, heptane
It can also be used after dissolving. The solid catalyst component (A) comprises component (a) and component (b)
 , Component (c), component (d) and component (e)
Prepared. This contact is an inert organic
Although it is possible to work in the absence of solvent,
Considering easiness, it is preferable to treat in the presence of the solvent.
Good. Hexane is used as the inert organic solvent.
Saturated hydrocarbons such as benzene, heptane and cyclohexane,
Aromatics such as zen, toluene, xylene and ethylbenzene
Hydrocarbons, ortho-dichlorobenzene, methylene chloride,
Halogenated hydrocarbons such as carbon chloride and dichloroethane
Among them, those having a boiling point of about 90 to 150 ° C.
Aromatic hydrocarbons, specifically, toluene, xylene,
Tilbenzene is preferably used. The amount ratio of each component is based on 1 g of component (a).
Component (b) is 0.01 to 10 g, preferably 0.05 to 2.0 g.
Component (c) is 0.1 to 200 ml, preferably 0.5 to 100 ml.
And component (d) is 0.01 to 1.0 g, preferably 0.1 to 0.5 g.
And component (e) is 0.01 to 1 g, preferably 0.05 to 5.0 g.
is there. In addition, the amount of inert organic solvent used is particularly limited.
Although there is no limitation, considering the operational problems, the component (c)
The volume ratio is preferably in the range of 0.1 to 10. Note that these
Components may be added separately at the time of contact, or one or two
It is also possible to select and use the above. The contact of each component is carried out in an inert gas atmosphere with water
Stir in a vessel equipped with a stirrer under the condition where
It is done while. The contact temperature is determined by simply contacting and stirring.
When denaturing by dispersing or suspending
May be in a relatively low temperature range around room temperature
However, when the product is obtained by the reaction after the contact,
A temperature range of 30 ° C. is preferred. Temperature during the reaction is less than 40 ° C
In the case of, sufficient reaction does not proceed, resulting in
The performance of the solid catalyst component became insufficient and exceeded 130 ° C.
If this occurs, the evaporation of the used solvent becomes remarkable,
Control becomes unstable. The reaction time is 1 minute or more.
Above, preferably 10 minutes or more, more preferably 30 minutes or more
It is. In preparing the solid catalyst component (A) of the present invention,
Component (a), component (b), component (c), component (d), and component (e)
, But the order of contact is not particularly limited and is optional.
However, when the contact order of each component is exemplified, it is as follows.
is there. 1.Contact components (a), (b), (c), (d) and (e) simultaneously.
Let 2.The components (a), (b), (c), (d) and (e)
The solid product thus obtained is brought into contact with the component (c) repeatedly. 3.The solid obtained by pre-contacting components (a), (b) and (c)
The components (d) and (e) are brought into contact with the body product. 4.The solid obtained by previously contacting the components (a), (b) and (c)
The components (d) and (e) are brought into contact with the
The return component (c) is brought into contact. 5.Pre-contact components (a), (c), (d) and (e)
The component (b) is brought into contact with the obtained solid product. 6.Pre-contact components (a), (c), (d) and (e)
The component (b) is contacted with the solid product
And contact component (c). 7.The components (a), (c), (d) and (e)
The component (b) is contacted with the solid product
The components (b) and (c) are brought into contact. 8.Pre-contact components (a), (b), (c), (d) and (e)
Repeated components (b) and (c) are added to the solid product obtained in
Make contact. In the order of contact of the above components, the contact of component (e)
The order of contact is arbitrary, but components (a), (c) and (d) are
Contact with the solid product obtained by contact
Low polymer fines content while maintaining polymer density
It is preferred to make In the above contact, the obtained solid
To the body product, repeat component (b) and / or component (c)
The contact conditions when contacting are in the temperature range of 40 to 130 ° C.
For at least 1 minute, preferably at least 10 minutes, more preferably 3 minutes.
Hold for at least 0 minutes. At this time, component (b) and component (c) were
As it is, or with the above inert organic solvent
There is a method of diluting appropriately and adding, but the latter method is used.
Is preferred. Obtained by the contact and reaction
The solid product was washed with the above-mentioned inert organic solvent.
Then, contact treatment with component (b) and / or component (c)
Is also one of the preferred embodiments. A specific example of the method for preparing the solid catalyst component (A) will be described below.
Shown below. 1. Component (a) in an aromatic hydrocarbon solvent such as toluene
Diethoxymagnesium and aluminum as component (b)
Is suspended in a temperature range of -10 to 30 ° C.
And add titanium tetrachloride as component (c) to the suspension.
You. At this time, the amount of titanium tetrachloride depends on the amount of solution in which component (a) is suspended.
It is preferable that the volume ratio with respect to the medium is 1/2 or less.
The suspension is heated, and the component (d) is heated in a temperature range of 40 to 100 ° C.
Dibutyl phthalate to the suspension as
Diethyl phthalate is added in a temperature range of 60 to 80 ° C.
Add dimethylpolysiloxane as component (e)
You. Further raise the temperature, and in the temperature range 100-120 ° C for 30 minutes
And then react for 3 hours to obtain a solid product. The solid raw
The product is washed with titanium tetrachloride diluted in toluene,
And washed with toluene. The temperature at this time is 40 to 130
It is 1 minute or more in the temperature range of ° C. Further toluene and tetrasalt
Titanium iodide is added to and brought into contact with the solid product, and the temperature is increased.
Hold at 100-120 ° C for 30 minutes to 3 hours to react
You. At this time, aluminum trichloride was again used as component (b).
A ride can also be added. Finally with heptane
The solid product is washed to obtain a solid catalyst component (A). 2.As component (a) in aromatic hydrocarbon solvents such as toluene
Suspension of diethoxymagnesium in temperature range -10 to 30 ° C
And add titanium tetrachloride as component (c). On this occasion
The amount of titanium tetrachloride is based on the solvent in which component (a) is suspended.
It is preferable that the capacity ratio is 1/2 or less. Then the ingredients
(d) Di-iso-octyl phthalate is used in a temperature range of 30 to
Add to the suspension at 60 ° C and add diethyl phthalate
Is added in the temperature range 60-80 ° C. Further raise the suspension
Dimethylpolysiloxane as component (e) in the temperature range
It is added at 80 to 100 ° C., and the temperature is further raised.
Hold at ~ 120 ° C for 30 minutes to 3 hours to react and produce solid
Obtain a product. The solid product was diluted in toluene and tetrachloride
Wash with titanium and then with toluene. At this time
Is 1 minute or more in a temperature range of 40 to 130 ° C. Next
Aluminum trichloride is added to the solid product as component (b).
A ride is added and brought into contact, and at this time, the component (b) is
Dissolve in an organic solvent such as toluene to make contact
It is preferable to add and contact with them. Further titanium tetrachloride
And then the temperature is raised, and in the temperature range 100-120 ° C.
The reaction is held for 30 minutes to 3 hours, and the solid is reacted with heptane.
The product is washed to obtain a solid catalyst component (A). The solid catalyst of the present invention prepared as described above
The medium component (A) is washed with an inert organic solvent such as heptane.
It is preferable to remove unreacted substances, and after washing, drying
Or after washing as it is,
Minium compound (B) [hereinafter referred to as “component (B)”
Yes] and organosilicon compound (C) [hereinafter referred to as “component (C)”
Olefins of the present invention in combination with
Form a polymerization catalyst. Organic aluminum used in the present invention
The compound (B) has the general formula R¹ _qAlY_3-q (Where R¹Is an alkyl group having 1 to 4 carbon atoms, and Y is water
Any of nitrogen, chlorine, bromine and iodine, and q is 0 <q
<3 is a real number. ) Represented by an organic aluminum compound
Object is used. Such organoaluminum compounds
(B) includes triethylaluminum, diethyla
Luminium chloride, tree iso-butylaluminum
Aluminum, diethyl aluminum bromide, ethyl aluminum
Hydride and the like.
Can be used. Preferably triethylaluminum, tree
iso-butylaluminum. Further, the organic silicon used in the present invention
The elemental compound (C) has the general formula R^Two _rSi (OR^Three)_4-r (Where R^TwoIs an alkyl group having 1 to 12 carbon atoms, cyclo
Alkyl group, phenyl group, vinyl group, allyl group, aral
It may be the same or different in any of the kill groups. R^ThreeIs
An alkyl group having 1 to 4 carbon atoms, a cycloalkyl group,
Any of a nyl group, vinyl group, allyl group, and aralkyl group
And may be the same or different. r is 0 or an integer from 1 to 3
Is a number. ) Is used.
You. Such organosilicon compounds (C) include phenyl
Alkoxy silane, alkyl alkoxy silane,
Nilalkylalkoxysilane, cycloalkylalco
Xysilane, cycloalkylalkylalkoxysila
And alkoxysilane. Specific examples of the above organosilicon compound (C)
Is a general formula used for the preparation of the solid catalyst component (A).
R⁸ _ySi (OR⁹)_4-yThe organosilicon compound represented by
The same thing as the thing can be used. Among them,
Di-n-propyldimethoxysilane, di-iso-pro
Pildimethoxysilane, di-n-butyldimethoxysila
, Di-iso-butyldimethoxysilane, di-t-butyl
Tyldimethoxysilane, di-n-butyldiethoxysila
, T-butyltrimethoxysilane, dicyclohexyl
Dimethoxysilane, dicyclohexyldiethoxysila
, Cyclohexylmethyldimethoxysilane, cyclohexane
Xylmethyldiethoxysilane, cyclohexylethyl
Dimethoxysilane, cyclohexylethyldiethoxy
Orchid, dicyclopentyldimethoxysilane, dicyclope
Dimethyldiethoxysilane, cyclopentylmethyldimethy
Xysilane, cyclopentylmethyldiethoxysilane,
Cyclopentylethyldiethoxysilane, cyclohexyl
Rucyclopentyldimethoxysilane, cyclohexyl
Clopentyldiethoxysilane, 3-methylcyclohexyl
Silcyclopentyldimethoxysilane, 4-methylcyclyl
Rohexylcyclopentyldimethoxysilane, 3,5-
Dimethylcyclohexylcyclopentyldimethoxysila
Preferably, the organosilicon compound (C) is
Can be used alone or in combination of two or more
You. In the polymerization method of the present invention, the solid
Catalyst component (A), organoaluminum compound (B) and
Olefin in the presence of a catalyst comprising an organosilicon compound (C)
Polymerize or copolymerize fins, but use each component
Quantitative ratios may be determined unless they affect the effects of the present invention.
It is usually, but not limited to, organic organic
The luminium compound (B) is a titanium compound in the solid catalyst component (A).
1 to 1,000, preferably in a molar ratio per mole of
Or 50 to 500, the organosilicon compound (C)
(B) From 0.0020 by mole per mole of the component
2, preferably used in the range of 0.01 to 0.5
You. Further, together with the above-mentioned organosilicon compound (C),
Organic compounds containing oxygen or nitrogen
You. Specific examples include alcohols, pheno
, Ethers, esters, ketones, acid halide
Compounds, aldehydes, amines, amides, nitriles
, Isocyanates, and the like. More specifically, methanol, ethanol
, Propanol, butanol, pentanol, hexa
Octanol, 2-ethylhexanol, dode
Alcohols such as canol, phenol, cresol, etc.
Phenols, methyl ether, ethyl ether,
Propyl ether, butyl ether, amyl ether, di
Ethers such as phenyl ether, methyl formate,
Chill, vinyl acetate, propyl acetate, octyl acetate, acetic acid
Cyclohexyl, ethyl propionate, ethyl butyrate,
Tyl benzoate, ethyl benzoate, propyl ben
Zoate, butyl benzoate, octyl benzoate
G, cyclohexyl benzoate, phenyl benzoate
G, p-methyl toluate, p-ethyl toluate, P-meth
Xyethyl benzoate, P-ethoxyethyl benzoate
Monocarboxylic acids such as methyl, methyl anisate and ethyl anisate
Acid ester, diethyl maleate, dibutyl maleate
Dimethyl, adipate, diethyl adipate, adipate
Dipropyl adipate, dibutyl adipate, dime adipate
Chill, diisodecyl adipate, dioctyl adipate
Dimethyl phthalate, diethyl phthalate, diphthalate
Propyl, dibutyl phthalate, dipentyl phthalate,
Dihexyl talate, diheptyl phthalate, dithiophthalate
Dica such as octyl, dinonyl phthalate, and didecyl phthalate
Rubonic esters, acetone, methyl ethyl ketone,
Butyl butyl ketone, acetophenone, benzophenone, etc.
Ketones, phthalic dichloride, terephthalic acid dichloride
Acid halides such as chloride, acetaldehyde, propio
Aldehyde, octyl aldehyde, benzaldehyde
Aldehydes such as methylamine, ethylamine, tri
Butylamine, piperidine, aniline, pyridine, etc.
Mines, acetonitrile, benzonitrile, tolunitrile
And the like. The method for producing an olefin polymer of the present invention
The solid catalyst component (A) as described above,
Compound (B) and organosilicon compound (C)
Olefin polymerization is carried out.
Polymerization ". Before we do)
Such preliminary polymerization (hereinafter sometimes referred to as “preliminary polymerization”)
You. )I do. In the prepolymerization, the solid catalyst component
(A) in combination with a part of the organoaluminum compound (B)
Used. At this time, all of the organosilicon compound (C)
Parts or parts can be used in combination with these components.
Wear. Regarding the contact order of each component when performing prepolymerization
Optionally, but preferably, the organic
Luminium compound (B) is charged, and then the solid catalyst component (A)
And then contacting one or more olefins
Make contact. When combining with an organosilicon compound (C)
In the pre-polymerization system,
(B), and then contact the organosilicon compound (C).
And then contact with the solid catalyst component (A).
Or contacting two or more olefins
No. Olefin using the combination catalyst as described above
Prepolymerization, in which the presence of inert hydrocarbon solvent
Perform in your presence. As the inert hydrocarbon solvent, propane,
Butane, pentane, hexane, heptane, octane, de
Can, dodecane, cyclohexane, benzene, tolue
, Xylene, mineral oil, etc. are used,
Among them, aliphatic carbonization such as hexane and heptane
Hydrogen is preferably used. In the prepolymerization of the present invention, nitrogen or
Inert gas such as argon or olefin for polymerization
Perform in an atmosphere of Inert hydrocarbon solvent as described above
When performing pre-polymerization in the presence of
Dissolve a small amount of the olefin to be prepolymerized. Specifically
Is an olefin that performs one or more prepolymerizations
To 0.01 to 1.0 g, preferably 0.1 g, per 1 g of the solid catalyst component (A).
03-0.5g, more preferably 0.05-0.3g inert hydrocarbon
Dissolve in solvent. At this time, the olefin dissolved in the solvent
Is 1 to 1 of the amount of the polymer finally formed in the prepolymerization.
50%, preferably 3 to 30%, more preferably 5 to
15%. Thus, first the olefin in the solvent
Dissolve the organic aluminum compound (B)
Next, the organosilicon compound (C) and then the solid catalyst component
After charging (A) and bringing it into contact, contact the specified amount of olefin
To carry out the pre-polymerization
Activity or stereoregularity and bulk ratio of formed polymer
Weight is improved, and the amount of polymer fine powder is reduced.
be able to. During the prepolymerization as described above, the organic aluminum
The titanium compound (B) is a titanium atom in the solid catalyst component (A).
0.5 to 50 mol, preferably 1 to 25 mol, more preferably
Preferably 2 to 10 moles of organic aluminum used in the main polymerization
It is desirable to use an amount smaller than the amount of the compound (B).
No. Reserve the above amount of organoaluminum compound (B)
When used during polymerization, it causes a decrease in catalytic activity. The organosilicon compound (C) is used for prepolymerization.
The amount of titanium used in the solid catalyst component (A)
0 to 10 moles, preferably 0 to 5 moles per atom, furthermore
Preferably it is in the range of 0 to 1 mol. The concentration of the solid catalyst component (A) in the prepolymerization
Is 0.1 per liter of the above-mentioned inert hydrocarbon solvent.
01 to 50 g, preferably 0.05 to 30 g, more preferably 0.
It is desirable to set it in the range of 1 to 15 g. Like this
In the pre-polymerization in the light,
Can be performed at concentrations much higher than the
Pre-polymerization, even in relatively small polymerization tanks
Becomes possible. The olefin used for the prepolymerization is described below.
The same as the olefin used in the main polymerization, or
May be different, ethylene, propylene,
4-Methyl-1-pentene, vinylcyclohexane
And the like, preferably ethylene or propylene.
is there. One of these olefins may be used,
A combination of more than one species may be used. The temperature at the time of performing the prepolymerization is from 0 to
40 ° C., preferably 5-35 ° C., more preferably 10-30 ° C.
It is. At temperatures below this range, olefin weight
Takes a long time and causes deterioration of the catalyst.
When the temperature rises above the range, the polymer formed dissolves in the solvent.
As a result, the catalyst performance during the main polymerization decreases
Resulting in. In addition, regarding the reaction time during pre-polymerization,
Can take enough time to produce a predetermined amount of polymer
Is usually 0.1 to 10 hours, preferably 0.5 to 2 hours.
You. In the prepolymerization of the present invention, the solid catalyst component
(A) 1 to 20 g, preferably 1.5 to 15 g, per 1 g
More preferably, a polymer in the range of 2 to 10 g is formed.
It is desirable to carry out. The amount of the produced polymer is less than this range.
If not present, the catalytic activity in the main polymerization decreases, and furthermore
The stereoregularity and bulk specific gravity of the produced polymer decrease, and
This causes an increase in the amount of fine powder of coalescence. Also from this range
When the amount of the polymer is large, the catalyst activity in the main polymerization decreases.
Causes troubles when processing the resulting polymer.
It may cause a problem. After performing the prepolymerization as described above,
The main polymerization described below is performed, but the pre-polymerized catalyst is
When preserving for a while, use as a solvent in the pre-polymerization described above.
The same inert hydrocarbons that are released into the solvent
Prepolymerization to the extent that no aluminum compounds can be detected
It is preferred to wash the catalyst. With this cleaning,
Deterioration of the performance of the polymerization catalyst can be suppressed. After performing the prepolymerization as described above,
Prepolymerization catalyst, organoaluminum compound (B) and
For the polymerization of olefins formed from organosilicon compounds (C)
The main polymerization of the olefin is carried out in the presence of a catalyst. This main polymerization
Is the homopolymerization of olefins or two or more olefins.
Random copolymerization or block copolymerization
It is. The amount ratio of each component affects the effect of the present invention.
Is arbitrary and particularly limited as long as it does not affect
However, the organoaluminum compound (B) is usually
1 to 50 per mole of titanium atoms in the solid catalyst component (A)
0 mol, the organosilicon compound (C) is equivalent to the mole of the component (B).
It is used in the range of 0.001 to 0.5. The order of contact of each component is arbitrary,
As in the contact sequence for the prepolymerization described above,
And the organoaluminum compound (B)
The solid catalyst component (A).
Preferably, the olefin is polymerized. The polymerization operation is carried out in the presence of an organic solvent.
It can be carried out in the presence of
It can be used in both body and liquid states.
The polymerization temperature is 200 ° C or lower, preferably 100 ° C or lower.
And the polymerization pressure is 10 MPa or less, preferably 5 MPa or less.
Below. In addition, either continuous polymerization or batch polymerization
Is also possible. Further, the polymerization reaction may be performed in one stage.
Alternatively, it may be performed in two or more stages. Polymerization or copolymerization with the catalyst according to the present invention
The olefins to be combined are ethylene, propylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene,
And these olefins are 1
Seeds may be used, or two or more kinds may be used in combination.
Good. [0068] EXAMPLES Hereinafter, examples of the present invention will be described in comparison with comparative examples.
Explain physically. Embodiment 1 <Preparation of solid catalyst component>
In a 500 ml round bottom flask equipped with a stirrer,
Sim magnesium 10g, aluminum trichloride 1.
0 g and 90 ml of toluene were inserted into the suspension. this
22 ml of room temperature titanium tetrachloride is charged therein and, with stirring,
The temperature was raised to 80 ° C. to cause a reaction. Next, the electron donating compound
3.3 ml of di-n-butyl phthalate and tetrabut
After adding 1.5 ml of xysilane, the temperature in the system was further raised to 110
The temperature was raised to ℃ and the reaction was carried out for 2 hours. After the reaction is complete, the supernatant is
And washed three times at 75 ° C. with 88 ml of toluene.
Was. After that, 89 ml of toluene and 22 ml of titanium tetrachloride were added.
In addition, treat with stirring at 100 ° C for 1.5 hours.
After that, the solid was washed 8 times with 83 ml of n-heptane at 40 ° C.
A medium component was obtained. Measure the Ti content in this solid catalyst component
As a result, it was 3.1 wt%. Also, the Al content is 0.8 wt%,
The content of the electron donating compound was 5.0% by weight. <Preliminary polymerization> After sufficiently drying with nitrogen gas,
Of 1500 ml of internal volume replaced with propylene gas
N-hepta in a stainless steel autoclave with a stirring device
300 ml of propylene gas, 50 ml of propylene gas
Lopylene was dissolved in n-heptane. Next, Triet
0.80 mmol of aluminum, and stirred for 30 minutes. So
After that, 0.12 mmol of the solid catalyst component as Ti was charged, and then
And propylene is continuously introduced, and while stirring, 3
Polymerization was carried out at 0 ° C. for 60 minutes. The amount of polymer produced is a solid catalyst
The weight was 4.8 g per 1 g of the component. <Main polymerization> Fully dried with nitrogen gas,
Stirring with an internal volume of 1800 ml replaced with propylene gas
N-heptane in a stainless steel autoclave
Charge 700ml and keep under propylene gas atmosphere
2, triethylaluminum 2.10 mmol, cyclohexyl
0.21 mmol of methyldimethoxysilane and the prepolymerization catalyst
Was charged as Ti in an amount of 0.0053 mmol to form a polymerization catalyst.
Then, 150 ml of hydrogen was charged, and the propylene pressure in the system was increased.
The polymerization was continued at 70 ° C. for 4 hours at 1.1 MPa. In addition, heavy
The pressure that decreases as the process proceeds is propylene only
Is supplied by continuously supplying a constant pressure during polymerization.
Held. According to the above polymerization method, the polymerization of propylene
The polymer produced is filtered off, dried under reduced pressure and solid weight
A coalescence was obtained. On the other hand, the filtrate is condensed and dissolved in the polymerization solvent.
A polymer was obtained, the amount of which was (A), and the amount of the solid polymer was (B)
And Further, the obtained solid polymer is boiled with n-heptane.
For 6 hours to obtain a polymer insoluble in n-heptane,
This amount is defined as (C). The polymerization activity (Y) per solid catalyst component is shown below.
It is expressed by an equation. (Y) = [(A) + (B)] (g) / Amount of solid catalyst component (g) Also, the attack occurrence rate (APP) is expressed by the following equation, (APP) = (A) (g) / [(A) + (B)] (g) The total crystalline polymer yield (t-II) is determined by the following equation. (t-II) = (C) (g) / [(A) + (B)] (g) Furthermore, the density (ρ) of the produced solid polymer, the melt index
Powder (MI) and bulk specific gravity (BD) and fine powder of 100 microns or less
When the amount was measured, the results shown in Table 1 were obtained.
Was. Embodiment 2 <Preparation of solid catalyst component>
In a 500 ml round bottom flask equipped with a stirrer,
Sim magnesium 10g, aluminum trichloride 1.
0 g and 90 ml of toluene were inserted into the suspension. this
20 ml of room temperature titanium tetrachloride is charged therein and, with stirring,
The temperature was raised to 50 ° C. to cause a reaction. Then di-iso-octi
After adding 4.5 ml of luphthalate, the temperature inside the system was further reduced to 11
After heating to 0 ° C and adding 1.0 ml of tetraethoxysilane,
The reaction was performed for 2 hours. After the reaction is completed, the supernatant is removed and
Washing was performed three times at 75 ° C. using 88 ml of ruene. Then
80 ml of ruene, 1.0 g of aluminum trichloride and four
Add 30 ml of titanium chloride and stir at 105 ° C for 2 hours
While reacting. Then, n-heptane 8 at 40 ° C.
After washing 8 times with 0 ml, a solid catalyst component was obtained. This solid catalyst
When the Ti content of the component was measured, it was 2.6 wt%.
The Al content is 0.7 wt%, and the electron donating compound content is 1.
It was 6 wt%. <Preliminary polymerization and main polymerization>
Using the solid catalyst component obtained,
The amount of ethyl aluminum used was 0.20 mmol, and
Diphenyl instead of xylmethyldimethoxysilane
Performed except for pre-polymerization using dimethoxysilane
Propylene was polymerized and evaluated in the same manner as in Example 1.
In addition, the results shown in Table 1 were obtained. Embodiment 3 <Preparation of solid catalyst component>
In a 500 ml round bottom flask equipped with a stirrer,
Sim magnesium 10g, aluminum trichloride 0.
8 g and 90 ml of toluene were inserted into the suspension. this
22 ml of room temperature titanium tetrachloride is charged therein and, with stirring,
The temperature was raised to 80 ° C. to cause a reaction. Then di-iso-octi
After adding 4.8 ml of luphthalate, the temperature inside the system was further reduced to 11
Heat to 0 ° C and add 1.5ml of vinyltriethoxysilane
Thereafter, the reaction was performed for 2 hours. After the reaction, remove the supernatant
Then, the mixture was washed three times at 75 ° C. with 88 ml of toluene. So
After that, 89 ml of toluene and 0.8 g of aluminum trichloride
And 22 ml of titanium tetrachloride, and add 1.5 ml at 100 ° C.
The reaction was performed while stirring for an hour. Then, n-f at 40 ° C
The solid catalyst component was obtained by washing 8 times with 83 ml of butane. this
When the Ti content in the solid catalyst component was measured, it was 2.2 wt%.
there were. The Al content was 1.0 wt%, and the electron-donating compound was
The weight was 2.9 wt%. <Preliminary polymerization and main polymerization>
Using the solid catalyst component obtained,
3.3 mmol of ethyl aluminum used, solid catalyst component
Is 0.83 mmol as Ti, and cyclohexylmethyl
Instead of rudimethoxysilane, cyclohexylcyclo
After performing pre-polymerization using pentyl dimethoxysilane
Other than that, polymerization of propylene was carried out in the same manner as in Example 1 and evaluated.
As a result, the results shown in Table 1 were obtained. Embodiment 4 <Preparation of solid catalyst component>
In a 500 ml round bottom flask equipped with a stirrer,
Insert 10 g of simmagnesium and 80 ml of toluene,
It was turbid. 20 ml of titanium tetrachloride at room temperature is placed in this.
Then, the mixture was heated to 50 ° C. with stirring to react. Next
After adding 5.2 ml of di-iso-octyl phthalate,
And add 0.2 ml of diethyl phthalate at 70 ° C
And then cyclohexylmethyldimethoxysilane 1.0m
After the addition of l, the temperature in the system was further increased to 112 ° C to
Allowed to react for hours. After the reaction is complete, remove the supernatant and
At 100 ° C. using 80 ml of ene and 20 ml of titanium tetrachloride
Treat for 15 minutes and wash 3 times with 100 ml of toluene
Was cleaned. Then 0.6 g of aluminum trichloride, torr
80 ml of ene and 20 ml of titanium tetrachloride were newly added and 10 ml
The reaction was carried out with stirring at 0 ° C. for 2 hours. Then, at 40 ° C
8 times with 100 ml of n-heptane to remove the solid catalyst component
Obtained. The Ti content in this solid catalyst component was measured.
And 2.1 wt%. The Al content is 0.6wt%,
The giving compound content was 3.2% by weight. <Preliminary polymerization and main polymerization>
Using the obtained solid catalyst component, cyclohexane
Silmethyldimethoxysilane to triethylaluminum
Except that 0.048 mmol was added and then prepolymerization was performed.
Forms a polymerization catalyst in the same manner as in Example 1,
When the polymerization was performed and evaluated, the results shown in Table 1 were obtained.
Obtained. Comparative Example 1 Aluminum trichloride and dimethyl polysiloxane
In the same manner as in Example 1 except that no
Preparation and polymerization of the solid catalyst component were performed. Result obtained
Are also shown in Table 1. Comparative Example 2 Before the pre-polymerization using the solid catalyst component prepared in Example 1
In the step, propylene is previously dissolved in n-heptane
Triethyl aluminum 30 under nitrogen atmosphere without
prepolymerization using 0.12 mmol of solid catalyst component as Ti
The polymerization was performed and evaluated in the same manner as in Example 1 except that
As a result, the results shown in Table 1 were obtained. [0082] [Table 1][0083] As is clear from the examples and comparative examples.
Propylene polymer produced by the method of the present invention
Has a density of 0.900 while maintaining high stereoregularity
Fine powder polymer in the range of 0.906 g / ml
Is also very low. Further
The polymer yield is also high, indicating that the method of the present invention
Is remarkably superior.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart schematically illustrating the present invention.

Claims (1)

(57) [Claims] (Claim 1) (A) General formula Mg (OR ⁴ ) ₂ (Formula
Wherein R ⁴ is an alkyl group or aryl having 1 to 4 carbon atoms
Represents a group. Alkoxy magnesium represented by)
(A) the following general formula I; Al (OR ⁵ ) _m X _{3 -m} (general formula I) (wherein R ⁵ is an alkyl group having 1 to 4 carbon atoms or
1 or 2 alkyl groups having 1 to 3 carbon atoms
Is a substituted aralkyl group, and when m is 2 or more, R ⁵ is
Same or different, X represents a halogen element, m is 0 ≦ m
≦ 3. ) And the following general formula II: R ⁶ _n AlX _3-n (general formula II) (wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms, and X is hydrogen)
Represents an atom or a halogen element, and n is 0 <n ≦ 3.
You. ) Selected from the group of aluminum compounds
At least one aluminum compound (b) represented by the general formula: Ti (OR ⁷ ) _p X _4-p (wherein R ⁷ is
X represents a halogen element, and p represents 0
Or an integer of 1 to 3. Halogenation represented by)
Titanium compound (c), electron donating compound (d) and
General formula R ⁸ _y Si (OR ⁹ ) _4-y (where R ⁸ is alkyl
Group, cycloalkyl group, phenyl group, vinyl group, allyl
Group or aralkyl group, which may be the same or different
No. R ⁹ is an alkyl group having 1 to 4 carbon atoms, cycloalkyl
Group, phenyl group, vinyl group, allyl group, aralkyl group
May be the same or different. y is 0 or
It is an integer of 1 to 3. ) And the following general formula (where x is
Represent the average degree of polymerization is from 2 to 30,000, R ¹⁰
R from the subject of R ¹⁷ is a methyl group, sometimes from R ¹⁰
Part of ¹⁷ is a phenyl group, hydrogen, higher fatty acid residue,
Substituted with a xy-containing group or a polyoxyalkylene group
Wherein R ¹³ and R ¹⁴ are methyl.
Including those forming cyclic polysiloxanes
No. Selected from the group of organosilicon compounds represented by
At least one organic silicon compound (e) ## STR1 ## And a solid catalyst component containing magnesium, titanium, an electron-donating compound, aluminum and halogen, and (B) a general formula R ¹ _q AlY _3-q (wherein, R ¹ represents a carbon number 1 to 4 alkyl groups, Y is any of hydrogen, chlorine, bromine and iodine, and q is 0 <q
<3 is a real number. And an organoaluminum compound represented by the formula (C): R ² _r Si (OR ³ ) _{4-r wherein} R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, R ³ may be the same or different, and may be any of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group and an aralkyl group. And r is an integer of 0 or 1 to 3). In a method for polymerizing olefins using a catalyst comprising an organosilicon compound represented by the formula (1), one or more olefins are used as solid catalysts. In the presence of an inert hydrocarbon solvent in which 0.01 to 1.0 g is dissolved per 1 g of component (A), the organoaluminum compound (B) and the solid catalyst component
(A) and, per titanium atom in the solid catalyst component (A),
The organoaluminum compound (B) is contacted in the range of 0.5 to 50 mol, and then one or more olefins are added so that the amount of the produced polymer per 1 g of the solid catalyst component (A) is in the range of 1 to 20 g. A method for producing an olefin polymer, which comprises carrying out main polymerization after preliminarily polymerizing in the range of 0 to 40 ° C.