JP3391583B2 - Olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] The present invention relates to a catalyst for olefin polymerization.
It is about. More specifically, the present invention
It uses a regular solid catalyst component, especially carbon
When applied to the polymerization of three or more olefins, high activity
In addition, a polymer with high stereoregularity can be obtained, especially with a small molecular weight.
Polymers (ie, polymers with a high MFR, such as
(Under 50 MFR)
Even if it is a polymer, it seems to have high stereoregularity
Related to a suitable catalyst. [0002] 2. Description of the Related Art Conventionally, titanium, magnesium, halogen
And, if necessary, a solid component containing an electron donating compound.
Minutes and the organoaluminum compound and, if necessary, the electron
Higher olefin polymerization catalyst composed of donor compounds
High tacticity in yield (ie, high catalytic activity)
It is known that a polymer having
You. Recently, when molding a polyolefin polymer,
In order to improve the molding cycle,
There is a demand for improved mold speed. For that, heavy
It is necessary that the molecular weight of the coalescence is small,
Even when is small, the same high stereoregularity is required
You. If it is not a highly stereoregular polyolefin polymer,
It is difficult to obtain sufficient performance required for the shape material, for example, rigidity
Because it is. However, with a conventionally known catalyst,
Indicates that the stereoregularity of the polymer that can be produced
It decreases with increasing MFR. For example, molecular weight comparison
In the case of production of a polymer having an extremely large size (for example, MFR = 1)
A polymer with high stereoregularity is obtained, but the molecular weight is small.
Manufacture (for example, MFR = 50 or more)
Conditions, the stereoregularity decreases and the high stereoregularity polymer
It is often difficult to obtain [0005] To solve the above problems,
For example, use a large amount of electron-donating compounds as external donors
In such a case, a large decrease in activity
And problems such as an increase in the cost of the catalyst are inevitable. [0006] SUMMARY OF THE INVENTION
The problem to be solved is to solve the aforementioned problems.
The light indicates that the molecular weight of the produced polymer is relatively small,
High activity with MFR of 50 g / 10 min or more
In addition, a new catalyst that gives a polymer with high stereoregularity
It is intended to provide a catalyst using a medium component. [0007] [Means for Solving the Problems] [Summary of the Invention] <Summary> The present inventors have proposed the use of a specific catalyst.
The present invention has been found to be able to solve the above-mentioned problems.
Reached. Namely, for olefin polymerization according to the present invention
The catalyst comprises the following components (A) and (B).
And the following. Component (A): titanium, magnesium, halogen and below
A silicon compound represented by the following general formula as an essential component
Solid components contained. Embedded image (Where R¹Together with the carbon atom adjacent to the silicon atom
A divalent hydrocarbon group forming a ring, R^Two, R^ThreeAnd R^Four
Is a monovalent hydrocarbon group, and n is 1 ≦ n ≦ 3
Numbers are shown). Component (B): organoaluminum compound [Effect] Novel solid catalyst component according to the present invention
Using a catalyst that uses high activity and high stereoregularity
Is obtained. Moreover, the molecular weight of the polymer is relatively small.
Where the MFR is 50 g / 10 min or
As described above, a polymer having high stereoregularity can be obtained.
The reason for this effect is currently unknown.
However, there is a solid catalyst composition containing a specific silicon compound component.
I think the point is to use minutes. [Specific description of the invention] <Olefin polymerization catalyst> Olefin polymerization according to the present invention
Catalyst comprises a specific component (A) and a specific component (B).
Things. Here, "consisting of" means that the component is
Only for indications (ie (A) and (B))
It does not mean that
Does not exclude coexistence of components. <Component (A)> Component used in the present invention
(A) is titanium, magnesium, halogen and general
formula Embedded image Containing the silicon compound represented by
Solid component. Where R¹Is adjacent to the silicon atom
A divalent hydrocarbon group that forms a ring with the hydrocarbon
R^Two, R^ThreeAnd R^FourIs a monovalent hydrocarbon group
And n is a number satisfying 1 ≦ n ≦ 3. Where T
i, Mg, halogen and silicon represented by the above general formula
This is called "contains as an essential component" for the compound.
This means that in addition to the four components of the list,
That each of these elements is
May exist as any compound, and
Elements may exist as interconnected
And When the component (A) used in the present invention is produced,
Solid containing titanium, magnesium and halogen
Components can be used, and known components can be used.
For example, JP-A-53-45688 and JP-A-54-3894.
No. 54-31092, No. 54-39483, No.
No. 54-94591, No. 54-118484, No. 54
No. 131589, No. 55-75411, No. 55-9
No. 0510, No. 55-90511, No. 55-1274
No. 05, No. 55-147507, No. 55-15500
No. 3, No. 56-18609, No. 56-70005,
No. 56-72001, No. 56-86905, No. 56
-90807, 56-155206, 57-3
No. 803, No. 57-34103, No. 57-92007
Nos. 57-121003, 58-5309,
58-5310, 58-5311, 58-87
No. 06, No. 58-27732, No. 58-32604
No. 58-32605, No. 58-67703, No.
58-117206, 58-127708, 5
Nos. 8-183708, 58-183709, 59
149905, 59-149906, etc.
The ones described are used. [0013] The magnesium source used in the present invention
Magnesium compounds
Ride, dialkoxymagnesium, alkoxymagne
Cium halide, magnesium oxyhalide, dial
Kill magnesium, magnesium oxide, magnesium hydroxide
And carboxylates of magnesium and magnesium. This
Among them, magnesium dihalide and dialkoxy
Magnesium is preferred. Further, a titanium compound serving as a titanium source is one of
General formula Ti (OR^Five)_4-pX_p(Where R^FiveIs hydrocarbon
A residue, preferably having about 1 to 10 carbon atoms;
Represents a halogen, and p represents a number satisfying 0 ≦ p ≦ 4)
Compounds to be used. As a specific example, TiCl
_Four, TiBr_Four, Ti (OC_TwoH_Five) Cl_Three, Ti (O
C_TwoH_Five)_TwoCl_Two, Ti (OC_TwoH_Five)_ThreeCl, Ti
(O-iC_ThreeH₇) Cl_Three, Ti (O-nC_FourH₉) C
l_Three, Ti (O-nC_FourH₉)_TwoCl_Two, Ti (OC_Two
H_Five) Br_Three, Ti (OC_TwoH_Five) (OC_FourH₉)_TwoC
1, Ti (O-nC_FourH₉)_ThreeCl, Ti (OC₆H
_Five) Cl_Three, Ti (O-iC_FourH₉)_TwoCl_Two, Ti
(OC_FiveH₁₁) Cl_Three, Ti (OC₆H₁₃) Cl_Three, T
i (OC_TwoH_Five)_Four, Ti (O-nC_ThreeH₇)_Four, Ti
(O-nC_FourH₉)_Four, Ti (O-iC_FourH₉)_Four, T
i (O-nC₆H₁₃)_Four, Ti (O-nC₈H₁₇)_Four,
Ti [OCH_TwoCH (C_TwoH_Five) C_FourH₉]_FourEtc.
I can do it. Further, TiX '_Four(Where X 'is a halogen
Molecular compound obtained by reacting an electron donor described later on
The material can be used as a titanium source. Such a minute
Specific examples of the child compound include TiCl_Four・ CH_ThreeCOC
_TwoH_Five, TiCl_Four・ CH_ThreeCO_TwoC_TwoH_Five, TiCl
_Four・ C₆H_FiveNO_Two, TiCl_Four・ CH_ThreeCOCl, T
iCl_Four・ C₆H_FiveCOCl, TiCl_Four・ C₆H_FiveC
O_TwoC_TwoH_Five, TiCl_Four・ ClCOC_TwoH_Five, TiC
l_Four・ C_FourH_FourO and the like. Also, TiCl_Three(TiCl_FourTo H_TwoReturn
Original, reduced with Al metal, or organic gold
Including those reduced with a genus compound), TiBr_Three, Ti
(OC_TwoH_Five) Cl_Two, TiCl_Two, Dicyclopentadi
Use of titanium compounds such as enil titanium dichloride
Is also possible. Among these titanium compounds, tetravalent titanium
Tan compounds, especially TiCl_Four, Ti (OC
_FourH₉)_Four, Ti (OC_TwoH_Five) Cl_ThreeAre preferred. Halogen is the above magnesium and
(Or) is supplied from a halogen compound of titanium
Common but other halogen sources, such as AlCl_Three,
AlBr_Three, Al (C_TwoH_Five) Cl_Two, Al (OC
H_Three)_TwoAluminum halides such as Cl and SiC
l_Four, Si (CH_Three) Cl_Three, Si (i-C_ThreeH₇)_Two
Cl _Two, Such as silicon halide, PCl_Five, Etc.
Halide, WCl_Five, MoCl_Five, Etc.
It can also be supplied from a known halogenating agent. The halogen contained in the catalyst component is
Hydrogen, chlorine, bromine, iodine or mixtures thereof
And chlorine is particularly preferred. [0019] Used in the present invention to produce component (A)
The silicon compound represented by the general formula Embedded image (Where R¹Together with the carbon atom adjacent to the silicon atom
A divalent hydrocarbon group forming a ring, R^Two, R^ThreeAnd R^Four
Is a monovalent hydrocarbon group, and n is 1 ≦ n ≦ 3
The compounds are represented by the following numbers: This
The iodine compound may be a mixture of two or more kinds.
No. The silicon compound represented by the above general formula is preferably
Is R¹Is a carbon atom adjacent to a silicon atom having 4 to 20 carbon atoms
A divalent hydrocarbon residue which forms a ring with an atom,
^TwoHas 1 to 20 carbon atoms, preferably 1 to 10 branched or
Is a linear saturated aliphatic hydrocarbon group. R^ThreeIs fat
Group hydrocarbon residue, preferably an aliphatic group having 1 to 10 carbon atoms
It is a hydrocarbon group. Specific examples of the silicon compound usable in the present invention
Is as follows. Embedded imageThe solid component used in the present invention is the above-mentioned essential component.
In addition to Al (O-iC_ThreeH₇)_ThreeAluminum compounds such as
And B (OCH_Three)_Three, B (OC_TwoH_Five)_Three, B
(OC ₆H_Five)_ThreeUse of other components such as boron compounds
It is also possible to use these materials such as aluminum and boron.
It may be left in the solid component as a component. Further, when producing this solid component,
Produced using a known electron donor as an internal donor
It is also a preferred embodiment. Electron donation usable for the production of this solid component
Alcohols, phenols as the body (internal donor)
, Ketones, aldehydes, carboxylic acids, organic acids and
And inorganic acid esters, ethers, acid amides, acid-free
Oxygen-containing electron donors such as waters, ammonia,
Donation of nitrogen-containing electrons such as nitrogen, nitrile and isocyanate
A body or the like can be exemplified. More specifically, (a) methanol, ethanol
Knol, propanol, pentanol, hexanol,
Octanol, dotecanol, octadecyl alcohol
Benzyl alcohol, phenylethyl alcohol,
C 1 -C such as isopropylbenzyl alcohol
18 alcohols, (b) phenol, cresol,
Xylenol, ethylphenol, propylphenol
, Isopropylphenol, nonylphenol, naph
6 to 2 carbon atoms which may have an alkyl group such as toll
5 phenols, (c) acetone, methyl ethyl keto
, Methyl isobutyl ketone, acetophenone, benzo
C3-C15 ketones such as phenone, (d)
Acetaldehyde, propionaldehyde, octylua
Aldehyde, benzaldehyde, tolualdehyde, naphtho
C2 to C15 aldehydes such as aldehydes,
(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate
Propyl acetate, octyl acetate, cyclohexyl acetate
, Cellosolve acetate, ethyl propionate, methyl butyrate
, Ethyl valerate, ethyl stearate, chloroacetic acid
Chill, ethyl dichloroacetate, methyl methacrylate,
Ethyl tonate, cyclohexane, ethyl carboxylate, ammonium
Methyl benzoate, ethyl benzoate, propyl benzoate, ammonium
Butyl benzoate, octyl benzoate, cyclohexyl benzoate
Sil, phenyl benzoate, benzyl benzoate, benzoic acid
Cellosolve, methyl toluate, ethyl toluate, g
Amyl ruylate, ethyl benzoate, methyl anisate
, Ethyl anisate, ethyl ethoxybenzoate, phthalate
Diethyl phosphate, dibutyl phthalate, diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
Phthalide, ethylene carbonate, etc. having 2 to 20 carbon atoms
Acid esters, ethyl (f) silicate, butyl silicate,
Phenyltriethoxysilane, t-butylmethyldimet
Xysilane, C_TwoH_FiveC (CH_Three)_TwoSi (OC
_TwoH_Five)_TwoInorganic acid esters such as silicates
(Excluding the silicon compound of the above general formula),
Tyl chloride, benzoyl chloride, toluic acid chloride
, Anisic acid chloride, phthaloyl chloride, isochloride phthalate
C2 to C15 acid halides such as Royl;
(H) Methyl ether, ethyl ether, isopropyl
Ether, butyl ether, amyl ether, tetrahi
Charcoal such as drofuran, anisole and diphenyl ether
Ethers having a prime number of 2 to 20, (ii) acetic acid amide,
Acid amides such as benzoic acid amide and toluic acid amide;
(Nu) methylamine, ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
Aniline, pyridine, picoline, tetramethylethylene
Amines such as diamine, (（) acetonitrile, ben
Nitriles such as zonitrile and tolunitrile
I can do it. These electron donors are for two or more
Can be. Of these, organic acids are preferred.
Steles, inorganic acid esters and organic acid halides,
Particularly preferred are phthalates and cellosolve acetate.
Steal, phthalic halides and silicates
You. The component (A) of the present invention comprises the above essential components
In addition to the above, optional components may be contained as necessary.
As appropriate, but with any suitable such optional components
Then, the following compounds can be mentioned. (A) Vinyl silane compound As the vinylsilane compound, monosilane (SiH_Four)
At least one hydrogen atom is vinyl (CH_Two= CH
Replaced by −) and one of the remaining hydrogen atoms
Some are halogen (preferably Cl), alkyl (preferably
Preferably having 1 to 12 carbon atoms, aryl (preferably
Is phenyl), etc.
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 (CH_Three)_Three, CH
_Two= CH-SiCl_Three, CH_Two= CH-SiCl_Two(C
H_Three), CH_Two= CH-SiCl (CH_Three) H, CH_Two
= CH-SiCl (C_TwoH_Five)_Two, CH_Two= CH-Si
(C_TwoH_Five)_Three, CH_Two= CH-Si (CH_Three) (C_Two
H_Five)_Two, CH_Two= CH-Si (C₆H_Five) (CH_Three)
_Two, CH_Two= CH-Si (CH_Three)_Two(C₆H_FourC
H_Three), (CH_Two= CH) (CH_Three)_Two-Si-OS
i (CH_Three)_Two(CH = CH_Two), (CH_Two= CH)_Two
SiCl_Two, (CH_Two= CH)_TwoSi (CH_Three)_Twoetc,
Can be exemplified. Of these, oxygen-containing
Vinyl silanes that do not have are preferred. (B) Organic gold of metals of groups I to III of the periodic table
Genus compound Examples of the organometallic compounds of metals of Groups I to III of the periodic table include:
It has at least one organic group-metal bond. In that case
The organic group has about 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
About 6 hydrocarbyl groups are typical. Valence
Organometallic compounds at least one of which is filled with an organic group
The remaining valence (if any) of the object metal is hydrogen
Atom, halogen atom, hydrocarbyloxy group (hydro
The carbyl group has about 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
Degree) or the metal (specifically,
Is -O-Al (CH) in the case of methylalumoxane_Three)
−) Satisfied with others. Specific examples of such organometallic compounds are given below.
Then, (a) methyllithium, n-butyllithium,
Organolithium compounds such as tributyl lithium,
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
Indicates that the organoaluminum compound is
Luminium compounds are preferred. The above optional components may be used alone or in combination of two or more.
Let it be used. Use these optional ingredients
Then, the effect of the present invention becomes larger. [0029]Production of component (A) Component (A) contains each component constituting component (A), or
If necessary, the above optional ingredients can be mutually
Contact, preferably in the middle and / or last
Washing with organic solvents such as hydrocarbons or halohydrocarbons
It can be manufactured by doing. In that case,
Solid product containing Ti, Mg and halogen as essential components
And then contacting it with a silicon compound of the above general formula
Or a two-stage method.
a solid product containing i, Mg and halogen as essential components
In the process of making this silicon compound already exists
Therefore, the method of producing component (A) at a stroke (in other words, one step
Method). The preferred method is the former
You. Contact of each component constituting the above-mentioned component (A)
Conditions are arbitrary as long as the effects of the present invention are recognized.
Although possible, the following conditions are generally preferred. Contact temperature
Is about -50 to 200 ° C, preferably 0 to 100 ° C,
It is. The contact methods include a rotary ball mill,
Mechanical, such as a
Method, contact by stirring in the presence of an inert diluent
Law. The inert diluent used at this time
Aliphatic or aromatic hydrocarbons and halocarbons
Hydrogen, polysiloxane and the like. The amount of each component constituting component (A) is
Can be arbitrary as long as the effect of the invention is recognized
However, generally, the following range is preferable. Titanium compound
The amount used is based on the amount of magnesium compound used.
1 × 10 in molar ratio^-FourGood within the range of ~ 1000
Or within the range of 0.01 to 10. As a halogen source
When using a compound for that purpose, the amount
Halo compound and / or magnesium compound
Magnesium to be used with or without Gen
1 × 10^-2~ 1000
Within the range, preferably within the range of 0.1 to 100
You. The amount of the silicon compound used is based on the component (A).
Atomic ratio of silicon to titanium component (silicon / tin
(Tan) 0.01 to 1000, preferably 0.1 to 10
0. When a vinyl silane compound is used,
The amount used is based on the amount of titanium component constituting component (A).
The ratio is preferably in the range of 0.001 to 1000, more preferably
More preferably, it is in the range of 0.01 to 100. Alminium
When using the boron and boron compounds, the amount used
The molar ratio of the magnesium compound is 1 to the amount used.
× 10^-3Within the range of 100, preferably 0.01
１1. When an electron donating compound is used, its use
The dosage is based on the amount of magnesium compound used.
1 × 10^-3It is preferably in the range of 10 to 10, preferably
It is in the range of 0.01 to 5. Component (B) The organoaluminum compound used in the present invention is as follows.
It is a compound represented by the general formula. R⁶ _3-mAlX_m (Where R⁶Has 1 to 20, preferably 1 to 12 carbon atoms
X is hydrogen or halogen, and m is 0
≦ m ≦ 2, respectively) Specific examples of such compounds include (a) trimethyl
Aluminum, triethyl aluminum, triisobuty
Aluminum, trihexyl aluminum, trioc
Chilled aluminum, tridecyl aluminum, etc.
Lialkyl aluminum, (b) diethyl aluminum
Monochloride, diisobutylaluminum monochlora
, Ethyl aluminum sesquichloride, ethyl alcohol
Aluminum alkyl such as luminium dichloride
Halide, (c) diethyl aluminum hydride,
Diisobutylaluminum hydride, among these
(A) Trialkylaluminum is preferred. The organoaluminums of (a) to (c)
The compound may include other organometallic compounds, such as R⁷ _3-qAl (O
R⁸)_q(Where 1 ≦ q ≦ 3, R⁷And R⁸Are the same
Or 1 to 20 carbon atoms which may be different, preferably 1 to
12 hydrocarbon residues)
A minium alkoxide can be used in combination. For example, triethyl aluminum and die
Combination with chill aluminum ethoxide, diethyl aluminum
Monochloride and diethylaluminum ethoxy
With ethyl aluminum dichloride and ethyl
Combined use with aluminum diethoxide, triethyl aluminum
And diethylaluminum ethoxide and diethyla
Combination with luminium chloride can be mentioned. Again
Lulumoxane, ethylalumoxane, isobutylalum
Alumoxanes, such as moxane, can also be used.
When an organoaluminum compound is used in combination,
It is preferable to use it in combination with alkyl aluminum. That is, (a)
And (b), (a) and (c), (a) and alkylaluminum
(A) and alumoxane. The amount of the component (B) used is determined by weight.
(B) / Component (A) is 0.1 to 1000, preferably 1
１００100. <Use of catalyst / polymerization> Catalyst according to the present invention
Is used for olefin polymerization. That is, the normal
Of course, it is applied to rea polymerization,
Liquid phase solventless polymerization without solvent (bulk polymerization), solution weight
It is also applicable to a combined or gas phase polymerization method. Also, continuous polymerization,
Also applicable to batch polymerization or prepolymerization
You. Hexane is used as the polymerization solvent for slurry polymerization.
, Heptane, pentane, cyclohexane, benzene,
Saturated aliphatic or aromatic hydrocarbons such as toluene
Alternatively, a mixture is used. The polymerization temperature is from room temperature to 150
℃, preferably 50-100 ℃, the polymerization pressure
Atmospheric pressure to 300 kg / cm^TwoDegree, preferably atmospheric pressure ~
50kg / cm^TwoAnd the molecular weight regulator at that time
Hydrogen can be used supplementarily. Further, the stereoregularity of the obtained polymer is controlled.
As a fourth component during polymerization, a known ester,
Use of electron-donating compounds such as ethers and amines
Can also. In the case of slurry polymerization, the amount of component (A) used
Is 0.001-0.1 gram, component (A) / liter
The range of the solvent is preferred. Α-Olefin polymerized with the catalyst system of the present invention
Are of the general formula R-CH = CH_Two(Where R is hydrogen or
Is a hydrocarbon residue having 1 to 10 carbon atoms and has a branched group
May be represented). Specifically,
Len, propylene, butene-1, pentene-1, hexene
Olefins such as 1,4-methylpentene-1
is there. Preferred are ethylene and propylene.
In addition to homopolymerization of these α-olefins, copolymerization,
For example, up to 30% by weight of propylene and propylene
Copolymerization with the above-mentioned olefins, especially ethylene.
I can. Other copolymerizable monomers (eg,
Copolymerization with cyclic olefins and diolefins)
You can also. The catalyst system of the present invention is used for the homopolymerization of olefins.
Or suitable for copolymerization, especially propylene alone or
When copolymerization is performed, the molecular weight is low, that is, the MFR is high.
50 to 300 g / 10 min, preferably 50 to 100 g
High stereoregulation even in propylene polymer / 10 min
Property is obtained. [0043] 【Example】 Example-1 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane
And then MgCl 2_TwoTo 0.4 mol and Ti
(O-nC_FourH ₉)_FourAt a temperature of 95 ° C.
Allowed to react for hours. After completion of the reaction, the temperature was lowered to 40 ° C.
Ide methylhydropolysiloxane (20 centistoke
48 ml), and react for 3 hours
Was. The resulting solid component was washed with n-heptane. About
Purify in the same manner as above into a flask
50 ml of n-heptane was introduced and synthesized as described above.
The solid component was introduced in an amount of 0.24 mol in terms of Mg atoms.
Then, SiCl was added to 25 ml of n-heptane._Four
Mix 0.4 mol and lead to flask at 30 ° C for 30 minutes
And reacted at 70 ° C. for 3 hours. After the reaction is completed,
Washed with butane. Next, as a silicon compound Embedded image Was introduced and contacted at 30 ° C. for 2 hours. contact
After the completion, thoroughly wash with n-heptane to obtain component (A).
Was. When a part was taken out and analyzed for composition, the Ti content
= 2.6 wt%, Embedded image Content = 9.7 wt%. [Polymerization of propylene] Stirring and temperature control
1.5 liter stainless steel
In the autoclave, fully dehydrated and deoxygenated n-hep
500 ml of tan, triethyl as component (B)
100 milligrams of aluminum
15 mg of the component (A) and then 400
Milliliter was introduced, and the temperature was raised and the polymerization pressure was increased to 5 kg /
cm^TwoG, polymerization temperature = 70 ° C, polymerization time = 2 hours
To perform a polymerization operation. After the polymerization, the obtained polymer
The slurry was separated by filtration and the polymer was dried.
As a result, 182.3 g of a polymer was obtained. Ma
The filtrate yielded 0.26 grams of polymer.
Was. From the boiling heptane extraction test, all products I.I. I (hereinafter T
-I. I) was 98.9 weight percent.
MFR = 71.6 g / 10 min, polymer bulk specific gravity = 0.4
It was 8 g / cc. Embodiment 2 [Production of Component (A)] Substituted with sufficiently purified nitrogen 5
In a 00 ml flask, add Mg (OC _TwoH_Five)_Two
20 grams, 100 milliliters of purified toluene
And then TiCl_Four  Introduce 60 ml, 7
The temperature was raised to 0 ° C, and then 3.2 ml of cellosolve acetate was added.
Torr, the temperature was raised to 100 ° C., and the reaction was performed for 3 hours. Anti
After completion of the reaction, the reaction product was thoroughly washed with n-heptane. That
Later, further TiCl_Four  Introduce 100 ml,
The reaction was performed at 110 ° C. for 3 hours. After the reaction is completed, n-hepta
After washing thoroughly with a solid, a solid for producing the component (A) is obtained.
The ingredients. As in the synthesis of component (A) in Example 1,
Add 50 milliliters of n-heptane to a well-purified flask.
And then 5 grams of the solid component obtained above,
As a silicon compound Embedded image 2.4 ml, and then Al (n-C₆H
₁₃)_Three1.8 g each, and at 70 ° C. for 2 hours
Contacted. After the contact is completed, wash thoroughly with n-heptane.
Thus, component (A) was obtained. When a part of the composition was analyzed,
Titanium content = 2.7 wt%, Embedded image Content = 11.8 wt%. [Polymerization of Propylene]
Except that the polymerization temperature was changed to 75 ° C.
Polymerization was performed in the same manner. 171.8 grams of polymer
And the T.I. I = 98.3 wt%, MFR = 49.
7 g / 10 min, polymer bulk specific gravity = 0.42 g / cc
Was. Examples 3 to 6 In the production of component (A) of Example-2, a silicon compound and
Then, except that the compounds shown in Table 1 were used,
Preparation of component (A) and polymerization of propylene
-2. Table 1 shows the results. Comparative Examples 1-2 In the production of component (A) of Example-1, a silicon compound
As in Example 1 except that the compounds shown in Table 2 were used.
Production of component (A) was carried out in exactly the same manner as
Was carried out in exactly the same manner. Table 2 shows the results. [0051] [Table 1] [0052] [Table 2] [0053]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 helps to understand the technical contents of the present invention regarding the Ziegler catalyst.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) Claims 1. An olefin polymerization catalyst comprising the following components (A) and (B). Component (A): a solid component containing titanium, magnesium, halogen, and a silicon compound represented by the following general formula as essential components. Embedded image (Where R ¹ is a divalent hydrocarbon group forming a ring with a carbon atom adjacent to a silicon atom, R ² , R ³ and R ⁴
Represents a monovalent hydrocarbon group, and n represents a number satisfying 1 ≦ n ≦ 3). Component (B): organoaluminum compound