JPS6272702A - Olefin polymerization catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst that provides a highly active polymer with good polymer properties.

Conventionally, when magnesium compounds such as magnesium halides, magnesium oxyhalides, dialkylmagnesiums, alkylmagnesium halides, magnesium alkoxides, or complexes of dialkylmagnesiums and organoaluminiums are used as carriers for transitional compounds such as titanium compounds, highly active catalysts can be obtained. It is known that many inventions have been proposed.

Furthermore, Ziegler type catalysts are well known as catalysts for stereoregular polymerization of olefins, and it is also well known that various methods have been proposed to further improve their activity and stereoregularity.

Among these various improvement methods, the method that has a particularly significant improvement effect on activity consists of introducing a magnesium compound into the solid component (Japanese Patent Publication No. 39 Sho.
-12105, Japanese Patent Publication No. 47-41676, and Japanese Patent Publication No. 47-46269). However, when olefins such as propylene are polymerized using catalysts produced by these methods, although the activity is very high, the stereoregularity of the resulting polymer is significantly reduced, and the olefin stereoregularity is significantly reduced. It is also known that its practical value as a polymerization catalyst is largely lost.

Therefore, a method has been proposed for improving the stereoregularity of the resulting polymer in olefin polymerization using a Ziegler-type catalyst containing a magnesium compound (Japanese Unexamined Patent Application Publication No. 1987-1998-1).
No. 9842, No. 50-126590, No. 51-577
Publication No. 89, etc.).

These methods are commonly characterized by avoiding further inclusion of an electron donor compound such as an ester or an amine in the solid catalyst component containing the titanium compound and the magnesium halide compound.

On the other hand, there is a method of adding a silicon compound, alcohol, etc. as a third additive in addition to an electron donor to a solid catalyst component (JP-A-50-108385, Ir1152-100).
596M, 52-104593, etc.) have also been proposed.

Although such a method considerably improves the activity and the stereoregularity of the produced polymer, it is still not enough to eliminate the steps of catalyzing the produced polymer and extracting the non-grade polymer. Furthermore, the properties of the produced polymer are also insufficient.

The present invention aims to provide a solution to the above-mentioned problems, and attempts to achieve the above-mentioned objects by using a catalyst composed of specific components.

In other words, the olefin Φ catalyst according to the present invention is characterized by being composed of the following components (A) to (D).

Component (A) A Ziegler catalyst solid component containing titanium, magnesium, and halogen as essential components.

Ingredients (8) Organoaluminum compound.

Ash 1 ko S”- A silicon compound having an S+-0-C bond.

It's 9th grade. A boron compound having a -0-C bond.

Effects When an olefin is polymerized using the solid catalyst component according to the present invention, a polymer having high activity and good stereoregularity can be obtained.

Furthermore, one of the features of the present invention is that when the catalyst according to the present invention is used, the polymerization rate pattern can be changed to tllm. Generally, when polymerization is carried out using a highly active catalyst, the activity is high in the initial stage of polymerization, and then the activity declines, which is often the case.

With this type of attenuation, depending on the polymerization conditions,
This is not preferable because the catalyst component may not be sufficiently released. When the solid catalyst component according to the present invention is used, the activity at the initial stage of polymerization can be suppressed, and so-called sustained type polymerization can be performed.

The catalyst of the present invention is composed of components (A) to (D).

Here, "composed of components (A) to (D>)" means that it is not only composed of components (A) to (D>) but also falls within the scope of the catalyst for olefin polymerization. This means that optional auxiliary ingredients can be included in the constituents (including when interpreting the scope of the claims).

One such auxiliary component is an electron donor compound.

"Composed of components (A) to (D)" does not mean only that components (A) to (D) are present in the catalyst of the present invention in the form of (as is). do not have.

If components (A) to (D) do not exist in the form of Zaru.

Component <A> Component (A) of the present invention contains Ti, Mq and CI as essential components, and can be used as a solid component (in other words, a transition metal compound component) of a Ziegler catalyst. Anything can be used. "Contains rTi, MO, and C1 as essential components" means that in addition to these three elements,
Other elements or components, such as electron donor compounds, as long as they do not impair their function as solid components of the Ziegler catalyst.
This means that it may contain. In addition, the electron donor compound in this case does not have to exist in the form as it is. Furthermore, the term "Ziegler catalyst" is intended to encompass Natsuta catalysts.

Such solid components (and their preparation methods) are well known, and are specifically described in, for example, JP-A Nos. 53-4, 5688, 54-3894@, 54-31092, and 54
-39483, 54-94591, 54-11
No. 8484, No. 54-131589, No. 55-754
No. 11, No. 55-90510, No. 55-90511, No. 55-127405, No. 55-147507,
No. 55-155003, No. 56-18609, No. 5
6-70005 R1fii No. 156-72001, No. 56-86905, No. 56-90807, No. 56-
No. 155206, No. 57-3803, No. 57-341
No. 03, No. 57-92007, No. 57-121003
No. 58-5309, No. 58-5310, No. 58
-5311, 58-8706, 58-2773
No. 2, No. 58-32604, No. 58-32605,
No. 58-67703, No. 58-117206, No. 5
No. 8-127708, No. 58-183708, No. 58
-183709, 59-149905, 59-
149906, - and the like can be exemplified.

The method for producing component (A) is described in many of the above-mentioned known publications, some of which are as follows.

(a) A method in which a magnesium halide, an electron donor compound, and a titanium-containing compound are co-pulverized and treated with a specific solvent.

(b) A method of treating alumina or magnesium with a halogenated phosphorus compound and contacting it with a magnesium halide, an electron donor compound, and a titanium halogen-containing compound.

(c) A method of avoiding contact of an electron donor compound, a titanium halide compound, and/or a silicon halide compound with a solid component obtained by contacting a magnesium halide, a titanium tetraalkoxide, and a specific polymeric silicon compound. In this case, it is preferable that the polymeric silicon compound has the formula -8i-0- and has a viscosity of about 1 to 100 centistics.

(d) A method of dissolving a magnesium compound with titanium tetraalkoxide and an electron donor compound and then contacting the solid component with a halogenating agent or a titanium halogen compound, which is then precipitated with a titanium compound.

Magnesium compounds used to produce the above component (A>) include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide,
Examples include magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like.

The titanium compound used to produce component (A>) has the general formula 4-0Xo (where R1 is Ti carbide (OR'), hydrogen residue, preferably one having about 1 to 10 carbon atoms, X represents halogen, and n is a number of 0≦n≦4.)
Examples include compounds represented by

As a specific example, Teha, T i G I T i B r
,1,.

TI(OC2to(5)C13, T!(OC2H5)2CI2, Ti(OC2H5)3C1, Ti(0-i C3to17>
Cl3, Ti(0-nc4119)Cl
3゜T i (0-nc4H9)2Cl 2, Ti
(OC2H5)Br3, T! (OC2H5) (OC4Hg)2CI, T
i (0-nC4Hg)3CI, Ti (0-061
-15>Cl3, T I (0-i C4Hg)2CI 2, Ti(QC
H) CI 5113' Ti(QCl-1)C13, Ti(OC2H5)4, Ti(0-nc3H7)4, Ti(0-nC4nC41-l, Ti(0-i C4Hg)4・Ti(0 -nCH) 6 13 4' Ti(0-nCH) 8 17 4ゝT I (OCH20H(C2H5) 04
There are 4 etc.

The titanium compound may also be a molecular compound obtained by reacting TiX' (where X' is halogen) with an electron donor. As a specific example, T1Cl ・CHCOC
2H5, TiCl ・CI-13G O202H5, Ti
Cl 4 ・C6 Tol 5 N ○ 2
, T1Cl ・CH3COCl, T i Cl 4 ・C6H3COC11T i Cl
, s・C6H5CO2C2H5, T1Cl ・CIC
Examples include OC2H5, T1Cl ・CHO, etc.

As mentioned above, when producing component (A), an electron donor compound can be added.

Electron donors that can be used in the production of the solid component (A) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acids, and non-I! II! i! Examples include oxygen-containing electron donors such as Class I esters, ethers, acid amides, and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. with a carbon number of 1;
to 18 alcohols, (b) 6 to 2 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol, etc.
(3) Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; (2) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, nathaldehyde, Aldehydes with 2 to 15 carbon atoms such as aldehyde and nathaldehyde, methyl (e)formate, 1111M methyl, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Ethyl stearate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, ocdyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate , ethyl toluate,
Amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, edyl xybenzoate, diethyl phthalate, dibutyl phthalate, heptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, Phthalide, ethylene carbonate, etc. with a total carbon number of about 2 to 20 [Nisdels, (to) ethyl silicate,
Non-if esters such as silicate esters such as butyl silicate and phenyltriethoxysilane, (t)acetyl chloride, penzoyl chloride, 1-ruyl chloride, anisyl chloride, phthaloyl chloride, iso-phthaloyl chloride Acid halides having 2 to 15 carbon atoms such as ,
(H) Ethers having a total of 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl ether, (S) Acids such as acetamide, benzoic acid amide, toluic acid amide, etc. Amides, (N) Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, (L) Nitriles such as acetonitrile, benzonitrile, tolnitrile, etc. types, etc. Among these, preferred are organic acid esters, inorganic acid esters, and acid halides. Two or more types of these electron donors can be used within each group or between each group.

The solid component (A) can also contain other components if necessary. For example, it can contain compounds such as silicon, aluminum, iron, zirconium, and zinc. Specifically, for example, S i CI 4
, (CH3) S i CI 3, (C2H5) SIC
13, (Cl1) S i CI A
I Cl 3.3 2 2゛AlBr FeCl Fec12.3゛
3゛Fe (OC2H5) 3, Z r
(QC41-19) 4, ZrCl
ZnCl etc. are al.

4. 2. Ingredient (B) Component (B) is an organoaluminum compound.

Specific examples of suitable organoaluminum compounds include 1 and △1x or 3-n n RAl(OR> (where R and R are 3-m
m is a hydrocarbon residue having about 1 to 20 carbon atoms or hydrogen, which may be the same or different; R4 is a hydrocarbon residue having about 1 to 20 carbon atoms; X is halogen; n and m are each Q<n<
3, a number where Q<m<3, and is expressed by .

Specifically, there are the following: (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b)-diethylaluminum monochloride, diisobutylaluminum monochlorite, ethylaluminum sesquichloride, Alkylaluminum halides such as ethylaluminum dichloride, (c) diethylaluminum hydride,
Aluminum alkoxides such as diisobutylaluminum hydride, (d) diethylaluminum ethoxide, and diethylaluminum phenoxide.

In addition to the above-mentioned aluminum compounds (a) to (c), other organic total compound compounds, such as and R5, may have a carbon number of 1 to 20 and may be the same or different.
It is a hydrocarbon residue of a certain degree. ) can also be used in combination with an alkyl aluminum alkoxide. For example, ] - combination of ethylaluminum and diethylaluminium ethoxide, combination of diethylaluminum monochlorite and diethylaluminium ethoxide, combination of ethylaluminum dichloride and ethylaluminum jetoxide, triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride. Can be used in combination with

Preferred components ((3) include triethylaluminum, tri-n-butyl-aluminum, tri-1-butylaluminum, tri-n-hexylaluminum, tri-n
- Trialkylaluminum such as octylaluminum and a combination system of these trialkylaluminum and alkylaluminum halide such as diethylaluminum chloride.

Any silicon compound having the structure D-8i-0-CMA can be used. Here, the remaining trivalent atoms of 3i are hydrogen, halogen (for example, chlorine), hydrocarbon residue (about 1 to 20 carbon atoms, preferably about 1 to 15 carbon atoms), halo, amino-1, or cyano- Substituted hydrocarbon residue (about 1 to 20 carbon atoms, preferably about 1 to 10 carbon atoms),
Ether oxygen-containing hydrocarbon residue (about 2 to 20 carbon atoms,
(preferably about 2 to 10), and others.

The remaining trivalent atoms of C include hydrogen, hydrocarbon residue (about 1 to 20 carbon atoms, preferably about 1 to 10 carbon atoms), halo,
Amino-1 or cyano-substituted hydrocarbon residue (1 carbon number
~20 or so, preferably 1 to 10 Pi! degree), ether oxygen-containing hydrocarbon residue (about 2 to 20 carbon atoms, preferably about 2 to 10 carbon atoms), and others.

In this compound, 3i and C may be bonded via these residues to form a ring.

Specific examples include (CH)Si(OH3)3, (CH)
S t (OCH3) 2, (CH=CH)Si
(QC (3) 3, CI (CH)
S i (OCH3) 3 , CI (CI-
1) Si (C)-()(OCH3)2゜Si(O
CH3)4, (Nu-13)Si(OC2H5)3, (C2H5)Si(OC2H5)3, (CH)Sl(OCH3)3, (01□H35)S I (CH)(OCH3)2, (
C2H5)23 i (OC2H5)2, CICM
Sl (OC2H5)3.1(C17L135)S i
(OCH3)3, (Cl-12= C old Si (C
I-13) (002 days 5) 2, S! (OC2H5)
4, (CH)Sl(OCH3)3, (CH)Si(OCH3)2,.

(C6115) (CH3)S! (OCH3>2, N
G (CH2)28! (OC2H5)3, H2N
(CH2)38 t (OC2H5)3, (OCH3)
3.

(06H5) S! (OC2H5) 3, (C6H
5) 2S! (OC2H5) 2, (C3H7)
S f (OC2H5) 3, (C6to1 5)
(CH3) 2 S t (OC2
I" 5), (Ct(3) S i
(OC3H7) 3 , (C6H5)CH
2Si(OC2H5)3, preferred among these are (Cto13)S i (OCH3)3, (
C2H5)Sl(OC2H5)3, (CH)Si(CH3)3, (C6H5)Sl(OCH3〉3, (C61]5)2S1(OCH3)3 (C61-15)S i (OC2H5) 3B and components < D) Any compound can be used as long as it has a B-0-C bond. The residues filling the remaining valences of B and C can be chosen from those described above for Si and C in component (C).

For example, B(OCH3)3, B OC2H5) 3, B(QC31-(7)
3, B (Oi C3H7)3, (0-nC4H9
) 3, B (OC6H13) 3, B (OC6H5) 3, B
(OC6H4CH3)3, B (OC2H5)2CI, B (OCH3)2CI,
Examples include (CH)B (OC2H5)2, (CH)B(OCH3)2, and B(OCH)CI. This 49
2 Among them, B(01'3)3, B(Q
Cl-4) B(OC3H7)3.2 5 3゛B(0-nC4H9)3, B(OC61-15) 3
, is.

Contact of Components (Δ) to Components (D) The catalyst of the present invention is formed by contacting Components (A) to Components (D). Although the components may be brought into contact under any conditions as long as the effects of the present invention are observed, the following conditions are generally preferred.

The quantitative ratio of each component is preferably within the following range. The used organoaluminum compound of component (B) is
) in a molar ratio of 1 to 1000 to the titanium component constituting the
It is better to be within the range of . The amount of component (C) used is preferably within the range of o, ooi to 10 in molar ratio to the amount of component (B) used. The amount of component (D) used is preferably within the range of 0.001 to 10 in molar ratio to the amount of component (B) used.

The order of contacting components (A) to (D) may be arbitrary as long as the effects of the present invention are observed, but the following methods are generally available.

Method 1: Component (B) → Component < A) → Component (C) → Component (D) Method 2: Component (B) → Component (C) → Component (A) → Component (D) Method 3: Component (D) ) → component (B) → component (C) → component (A) Method 4: component (C) → component (D) → component (B) → component (A> Among these, method 3 is preferred.

±Small Ni<>(/SoLPolymerized OlefinThe olefin polymerized by the catalyst system of the present invention has the general formula R-C
A typical example is H=CH2 (here, 1) is a hydrogen atom or a hydrocarbon residue having an FA prime number of 1 to 10, and may have a branching group. Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, and hexeno-1,4-methylpentene-1. Preferred are ethylene and propylene.

In the case of these polymerizations, copolymerizations can be carried out with up to 50 weight percent, preferably 20 weight cents, of the above olefins, based on ethylene, and up to 30 Lffi percent, based on propylene, of the above olefins,
In particular, ethylene and its copolymerization can be carried out. Copolymerization with other copolymerizable monomers (eg vinyl acetate, diolefins) can also be carried out. therefore,
Using the catalyst system of the present invention, for example, random and block copolymers of propylene and ethylene and/or butene-1 can be efficiently produced.

The catalyst system of the present invention can of course be applied to ordinary slurry polymerization, but it can also be applied to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. Applicable. It is also applicable to continuous polymerization, batch polymerization, or terminal polymerization. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and i-luene may be used alone or in combination. The polymerization temperature is from room temperature to about 200°C, preferably from 50°C to 150°C.
℃, and hydrogen can be used as an auxiliary molecular weight regulator at that time.

Support - 1 Example - 1 Formation (A'5) 40 stainless steel balls of 12 #Rφ were filled in a 0.4 liter ball mill that had been thoroughly dried and purged with nitrogen, and 20 g of MqCl 2 was added. Dihebutyl phthalate 15.
5 ml was introduced and ground in a rotary ball mill for 18 hours. After the pulverization was completed, the mixed pulverized composition was taken out from the mill in a dry box. Subsequently, 8.8 g of the pulverized composition was introduced into a flask that had been sufficiently purged with nitrogen, and 25 ml of n-heptane and 125 ml of TiC were introduced into the flask, followed by a reaction at 100° C. for 3 hours.

After the reaction was completed, it was thoroughly washed with n-hebutane. When a portion of the solid component was taken out and analyzed for composition, the T1 content was 3.01 bar/1-.

In a stainless steel autoclave with an internal volume of 1.5 liters and equipped with a stirring and temperature control device, 500 ml of thoroughly dehydrated and deoxidized n-hebutane was added.
125 mg of ethylaluminum (component (B)), 8.1 mg of diphenyldimethoxysilane (component (C)), 4.3 mg of diethyl borate (component (D)) and 15 mg of component (A) synthesized above. Next, 60 milliliters of H2 was introduced, the temperature and pressure were increased, and polymerization was carried out under the conditions of a polymerization pressure of 5 Kg/ci G, a polymerization temperature of 75°C, and a polymerization time of 2 hours. After the completion of polymerization, The resulting polymer slurry was separated by t-filtration, and the polymer was dried.

150.2 grams of polymer was obtained. Meanwhile, 1.4 grams of polymer was obtained from the filtrate.

From the boiling hebutane extraction test, all products were found to be 1.1 (hereinafter T-1).
, 1 and abbreviated t> were 96.1 times 51 bart:z bar. VFR=3.1 (g/10 min), polymer bulk specific gravity=
It was 0.37 (g/cc).

Comparative Example-1 Under the m-matching conditions of Example-1, B(OC
The procedure was carried out in exactly the same manner except that 2H5)3 was not used. 132.7 grams of polymer were obtained, r-
1, I=90.5, VFR=11.8 (g/10 min)
, polymer bulk specific gravity=0.34 (g/cc).

Example 2 Synthesis of component (A) 100 ml of dehydrated and oxygenated n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then 0.1 mol of MaCl 2 and 48 g of Ti (0-nC) 4 were added. 9 after introducing O-2 mole
The reaction was carried out at 5°C for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 12 milliliters of methylhydroborisiloxane (20 ton stokes) was introduced and the reaction was allowed to proceed for 3 hours. The solid component produced was washed with n-hebutane. Next, 50 milliliters of n-heptane purified in the same manner as above was introduced into the flask which had been sufficiently purged with nitrogen, and 0.03 cells of the solid component synthesized above was introduced in terms of lVtg atoms. Then add 25 ml of n-hebutane to 5
0.05 mol of iCI was mixed and introduced into the flask at 30°C for 30 minutes, followed by reaction at 70°C for 1 hour. After the reaction was completed, it was washed with n-hebutane.

Next, 0.004 mol of dihebutyl phthalate was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 70°C for 30 minutes, and reacted at 70°C for 1 hour. After the reaction was completed, it was washed with n-hebutane.

Then 25 ml of T1Cl was introduced and 1
The reaction was carried out at 00°C for 3 hours. After the reaction was completed, the product was thoroughly washed with n-heptane to obtain the component (A) of the present invention. The Ti content in this component (A) was 2.54 weight percent.

Under the polymerization conditions of Propylene Polymerization Example-1, the above-produced product was used as component (A), 5.4 mg of diphenyldimethoxysilane was used as component (C), and 8 (OCI-1) was used as component (D). ) Polymerization of propylene was carried out in exactly the same manner except that 6 mDram was used. 211.9
grams of polymer were obtained, T-1,1 = 97.2 weight percent, VFR = 2.7 (g/10 min), polymer bulk specific gravity = 0.46 (g/cc).

Polymerization of propylene was carried out in exactly the same manner as in Example 2, except that diphenyldimethoxysilane as component (C) was not used.

169.3 grams of polymer were obtained, T-1,1=7
1.4 weight 4%, MFR=13.21/10 minutes)
, polymer bulk specific gravity -0.36 (g/cc).

Comparative Example-3 Under the polymerization conditions of Example-2, component (D) B(OC
Polymerization of propylene was carried out under exactly the same conditions except that H3)3 was not used.

186.2 grams of polymer were obtained, T-1, I=8
3.4Φ hanging base l~, MFR=16.5 (g/1
0 minutes), and the bulk specific gravity of the polymer was 0.41 (g/CC).

Example 3 Synthesis of component (A) MOCI2 was obtained by contacting Ti(0-nCH) methylhydroboricyl 494ゝloki→non (20 centistokes) in exactly the same manner as in Example 2. The solid component was introduced into the flask in exactly the same manner as in Example-2. Next, 140.05 mol of 5iC was introduced at 30°C for 1 hour, and the mixture was reacted at 80°C for 2 hours. After the reaction was completed, it was washed with n-hebutane. Then n-heptane 25
0.00 orthophthalic acid chloride per milliliter
Mix 4 moles, introduce at 30°C for 30 minutes, and heat to 70°C.
The reaction was carried out for 21R. After the reaction was completed, it was washed with n-hebutane. Then 125 ml of TiC was introduced,
The reaction was carried out at 100°C for 3 hours.

After the reaction is completed, the component (A
) was obtained. The l-i content in this component (A> is 2.77
[It was i percent.

Polymerization of Propylene In the polymerization of propylene in Example 2, polymerization of propylene was carried out under exactly the same conditions except that the amount of diphenyldimethoxysilane used as component (C) was changed to 2.6 milligrams. 203.4 grams of polymer were obtained, T-
1, I=96.2 Weight-Sen1-1MFR=4.9 (
g/10 min), polymer bulk specific gravity = 0.44 (g/cc
)Met.

Fruit/Ilj@-4 Dehydrated and deoxygenated n in a flask that was sufficiently purged with nitrogen.
- introduce 100 ml of hebutane, then MoC
0.1 mol of 13 and 0.2-E mol of T i (0-nc4H9)4 were introduced, and the mixture was reacted at 95° C. for 2 hours. After the reaction was completed, the temperature was lowered to 35° C., 15 milliliters of 1.3.5.7-tetramethylcyclotetrasiloxane was introduced, and the mixture was reacted for 5 hours. The solid component produced was washed with n-hebutane. Next, 50% of n-hebutane was added to a flask that had been sufficiently purged with nitrogen.
0.03'f of the solid component synthesized above was introduced using Mg atom exchange. Then S i C
Introducing 1, so, 06 mol in 30 minutes at 20°C 1.50
The reaction was carried out at ℃ for 3 hours. After the reaction was completed, it was washed with n-hebutane to obtain a component (△). The Ti content in component (A) is
The weight ratio was 4.52.

In the polymerization of propylene in Example-1, the component (C
Polymerization of propylene was carried out in exactly the same manner except that 10 mg of phenylethoxysilane was used as component (D) and 38.4 mg of B(OC4H9) was used as component (D). 104.1 grams of polymer were obtained, T-1,r=
94.3 market weight percent, VFR=6.7 (g/10
), and the bulk specific gravity of the polymer was 0.41 (9/cc).

Comparative Example-4 Under the polymerization conditions of Example-4, B(
Polymerization of propylene was carried out in exactly the same manner except that OC41-19)3 was not used.

84.5 grams of polymer were obtained, T-1,1=81
．． 6 market weight percent, MFR=9.8 (g/10 min)
, polymer bulk specific gravity -0.38 (g/cc).

In the production of component (A) of Example-3, ortho-C6
)-14 (COC+ )2 instead of CI-(COOC
The production was carried out in exactly the same manner except that 2+-+5 was used. Ti content was 2.977 percent by market weight.

Polymerization of Propylene In the polymerization of propylene in Example-1, as component (C) (C171135)S l <0CH3)3 12.5
Polymerization of propylene was carried out in exactly the same manner except that 36.8 milligrams of B (OC2H5) was used as component (D). 116
．． 9 grams of polymer are weighed 10, 1--1.1=94
．． 1 market weight percent, MFR=5.1 (g/10 min)
, polymer bulk specific gravity=0.42 (9/cc).

In the production of component (A) of Example-3, ortho-C6
S i (OC21−
15) The production was carried out in exactly the same manner except that 0.003 mol of 4 was used. The Ti content was 2.84%.

Polymerization of Propylene In the polymerization of propylene in Example-1, 217 mg of triisobutylaluminum was used as component (B), 10 mg of phenyltrimethoxysilane was used as component (C), and 6 mg of B (OCI-1) was used as component (D). Polymerization was carried out in exactly the same manner except for using the following.

92.3 grams of polymer were obtained, T-1,1-94
, 8 vehicle length percent, VFR = 7.7 (g/10 min)
, polymer bulk specific gravity=0.40 (g/cc).

Polymerization of propylene was carried out in exactly the same manner as in Example 2, except that the chassis temperature was changed to 70°C and 80°C. The results are shown in Table-1.

Example-8 Production of component (A) In the production of component (A>) of Example-3, ortho-C6
Cyclo-〇6H1o(C
The production was carried out in exactly the same manner except that OCl)2 was used. The Ti content was 2.41% by weight.

Under the polymerization conditions of Propylene Polymerization Example-3, component (C) was (0
Instead of 6H5)2S i (OCH3)2,
(Cto1) S i (OC2
H5) Polymerization of propylene was carried out in exactly the same manner except that 312 mg was used. 119.2 grams of polymer was obtained, T-i I = 94.2 weight percent, MFR = 6.8 (g/10 min), polymer bulk specific gravity = 0.42 (Si/CC).

Examples 9 to 11 Using component (A) produced in Example 3, propylene was polymerized using component (C) and component (D) shown in Table 2. The results are shown in Table-2.

Claims (1)

[Scope of Claims] An olefin polymerization catalyst comprising the following components (A) to (D). ¥Component (A)¥ Ziegler catalyst solid component containing titanium, magnesium, and halogen as essential components. ¥Component (B)¥ Organoaluminum compound. ¥Component (C)¥ A silicon compound having a Si-O-C bond. ¥Component (D)¥ A boron compound having a B-O-C bond.