JPS58183709A - Catalytic component for polymerizing olefin - Google Patents

Abstract

PURPOSE:The titled catalyst providing a polymer having high stereospecificity and good polymer properties, obtained by blending a solid composition consisting of a Mg dihalide, a Ti tetraalkoxide, and a silicon compound polymer with an electron donor and a halogen-containing compound. CONSTITUTION:(A) A solid composition consisting of a magnesium dihalide (e.g., magnesium chloride, etc.), a titanium tetraalkoxide (titanium tetraethoxide, etc.) and a silicon compound polymer (e.g., methylhydropolysiloxane, etc.) having a structure shown by the formula (R is hydrocarbon) is brought into contact with (B) an electron donor compound (e.g., ethyl benzoate, etc.) and (C) a halogen- containing compound (e.g., titanium tetrachloride, etc.), to give the desired catalytic component.

Description

Detailed Description of the Invention [1] Background of the Invention 1) Technical Field The present invention relates to a catalyst component that provides a highly active polymer with good polymer properties.

Conventionally, magnesium compounds, such as magnesium halide, magnesium oxyhalide, -)alkylmagnesium, alkylmagnesium halide, magnesium alkoxide, or lead bodies of dialkylmagnesium and organoaluminium, have been used as carriers for titanium compounds and transition gold-tin compounds. It is known that this will result in a highly active catalyst, and many proposals have been made.

In general, these prior art techniques have a certain degree of catalytic activity, but the polymer properties of the produced polymers are not sufficient, so improvements are desired. Polymer properties are extremely important in slurry polymerization, gas phase polymerization, and the like. If the polymer properties are poor, it may cause polymer adhesion within the polymerization tank, failure to extract the polymer from the polymerization tank, etc. Further, the polymer concentration in the polymerization tank is closely related to the polymer properties, and unless the 4-reamer properties are good, the # degree of the polymer in the polymerization tank cannot be increased. It is extremely disadvantageous in industry that the I-rimer has a high degree of birch.

2) According to the prior art patent publication No. 51-37195! By reacting titanium tetraalkoxyyt with Danesium halide etc.,
Furthermore, a method of carrying out an organoaluminum halide yt-reaction has been proposed. According to Japanese Unexamined Patent Publication No. 54-16393, a method is proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide or the like, and further a compound containing nitrogen and a reducing compound are reacted. However, according to the knowledge of the present inventors, when olefins such as ethylene are polymerized using catalysts produced by these methods, although the catalytic activity shows a certain value, the properties of the produced polymer are not good.

Olefin Stereoregular Electrochemical Catalyst 8 Ziegler type catalysts are well known, and it is also well known that various methods have been proposed to further improve their activity and stereogenic properties. Among these various improvement methods, a method that has a remarkable effect on improving the activity is one that consists of completely introducing a magnesium compound into the solid component (+1? Publication No. 12105, No. 12105, Special Feature). Kosho 47-41
676 and Japanese Patent Publication No. 47-46269). However, when olefins such as propylene are synthesized using catalysts produced by these methods, although the activity shows a very high value, the stereoregularity of the resulting polymer decreases significantly, and the olefin stereoregularity It is also known that there is a large loss of polymerization as a polymerization catalyst.

Therefore, in olefin polymerization using a Ziegler type catalyst containing a magnesium compound, various methods have been proposed to improve the stereoregularity of the resulting polymer ('4 Kai-Sho No. 47-9842, Kai-Kai-12 Fi 590, and Publications No. 51-57789, etc.).

These methods are commonly characterized in that an electron donor such as an amine or an ester is further contained in a solid @media component containing a titanium compound and a magnesium halide compound. Furthermore.

As is known from Japanese Patent Application Laid-Open No. 53-45688, a method for improving the τ filtration by treating a solid component formed by combining a titanium compound, a magnesium halide compound, and an electron donor with an interhalogen has also been proposed.

On the other hand, there is a method of adding a silicon compound, alcohol, etc. as a third additive in addition to the electron donor to the solid catalyst component (t4!
No. 0596, No. 52-104593, etc.), and improved methods of adding aluminum, germanium, or tin compounds have also been proposed (Japanese Patent Laid-Open No. 52-874).
Publication No. 89).

Although such a method improves the activity and the stereoregularity of the produced polymer to a considerable extent, it still obviates the need for decatalyzing the produced polymer and extracting the amorphous polymer.
It is understood that this has not yet been achieved. It is also understood that the properties of the produced polymer are not sufficient.

[11 @ Outline of Ming l) Does the present invention solve the above points? This purpose is intended to be avoided by using a mutually beneficial four-metal transfer catalyst component made from Tokden's reptile.

It is.

A solid composition consisting of a polymeric silicon compound having the components (Al, magnesium dihalide, titanium tetraal, where R is a hydrocarbon residue).

Ingredients (Bl Electron donating compound.

, fiffi minutes (C) Halogen-containing compounds.

2) Effects When α-olefin polymerization is carried out using the solid @ medium component according to the present invention as the 44-karat gold component of the Ziegler catalyst,
A polymer with high activity and excellent polymer properties is obtained. The reason why a polymer with high activity and good IJ polymer shape can be obtained is not necessarily clear, but it is due to the chemical interaction of the components used in the present invention and the special characteristics of the solid component (A) used and the catalyst component produced. This is thought to be due to its characteristic nature.

[1111 Detailed Description of the Invention 1, Component (A) 1) Composition Component (A) is a solid composition composed of magnesium dihalide, titanium tetraalkoxy P, and a specific polymeric silicon compound.

This solid composition (A) is neither a magnesium dihalide nor a complex of magnesium dihalide and titanium tetraalkoxide, but is another solid. At present, the contents have not been sufficiently analyzed, or according to the compositional analysis results, this solid composition is titanium, magnesium, halogen, and silicon? The molar ratio of halogen to magnesium is 0.4 or more and less than 2, preferably 1.0 to 1.8.
It appears to be a different compound from Schiff's magnesium oxide used as a raw material. This ingredient (
The specific surface area of A) is often small, usually 10 m/g.
and most of them are less than or equal to 3n+2/. Also,
According to the results of X-machine diffraction, dino-rosinide 1gnesium e seems to be a different compound from magnesium dihalide.

2) Production component (A) is produced by mutual contact of magnesium dihalide, titanium tetraalkoxide and certain polymeric silicon compounds.

(11,) Magnesium halide, for example, MK
There are F2, MgC 12, MgBr2, etc.

(2) Titanium tetraalkoxy, for example, T I (OC2H5) 4, T 4 (0
- 1 aoc3H7) 4, TI (o-nc4Hg
)4, TI(0-nC3H7)4, TI
(0-i m oC4 Hg)4, T I (0-
CH2Cl((CH3) 2) 4,TI(0-C(
C) (3) 3) 4, T i (0-C5H1 1) 4,
Ti(0-C6H13)4, TI(0-nc7H15
)4, T I C0CH (C3H7 )214, Tl
(OCH(CH3)C,aI(g)4,TI(OC
sH17)4, Tt(O810)(21)4.

T l (QC) (2CH (C 2H5 )C4H
There are g14 etc.

(3) Polymer silicon compound ― There are about 1 to 6 hydrocarbon residues.

Specific examples of polymer properties 1) compounds having such structural units include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane,
Examples include cyclohexylhydropodisiloxane.

The degree of polymerization is not particularly limited, but considering handling, the viscosity is between 10 centistokes and 10 centistokes.
It is preferable to have a value of about 0 centistokes. Furthermore, although the terminal end of the hydropolysiloxane does not have a large effect, it is desirable to block it with an inert group or a triplekylsilyl group.・ (4) Contact (amount ratio) of each component The stool t of each component is as long as the effect of the present invention is taken into account.
Although it may be arbitrary, it is generally preferably within the following range.

The amount of titanium tetraalkoxide to be used is within the range of 0.1 to 10 (preferably within the range of 1 to 4) in terms of molar ratio of 1 to magnesium dino-logenide.

The amount of polymer silicon compound used is IXI (1- to 1001
It may be within the range of , preferably within the range of 0.1 to 10.

(Contact method) Component (A) of the present invention can be obtained by contacting the three components described above to obtain 1. Contact of the three components is generally
This can be done in any way that is provided.

Contact may be made within the range of -100°C to 200°C, preferably 0°C to 70°C. The contact time is usually about 10 minutes to Δ) hours, preferably 0.5 to 5 hours.

It is preferable that the three components be brought into contact with each other under stirring, and by mechanical grinding using a Zeel mill, a shaking mill, etc.
It can also be brought into contact. 111F of 3-component contact! ;
may be of any type as long as the effects of the present invention are recognized, but it is common to bring the dihalogenated magnesium into contact with the titanium tetraalkoxide 1r, and then contact the polymeric silicon compound.

Contacting the three components can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium in this case include hydrocarbons, halogenated hydrocarbons, dialkylpolysiloxanes, and the like.

Specific examples of hydrocarbons include hexane, heptane, toluene, xylene, cyclohexane, etc. Specific examples of halogenated hydrocarbons include n-butyl chloride, 1.2-
Examples include dichloroethylene, carbon tetracarbon, chlorobenzene, etc., and specific examples of dialkylpolysiloxane include trimethylpolysiloxane, methyl-phenylpolysiloxane, etc.

2. Ingredient (B) Component (Bl is an electron donating compound.

1) Carzenate ester This is one of the preferable electron-donating compounds for use in the present invention. Examples of organic acid esters include aliphatic carcinic acid esters and aromatic carzenic acid esters.

(a) Those commonly used as aliphatic carbenoic acid esters are derived from saturated or unsaturated aliphatic monocarzenic acids having 1 to 12 carbon atoms and monohydric alcohols having 1 to 12 carbon atoms. It is a carzenic acid ester. Specific examples include ethyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, and octyl laurate.

Oki) A commonly used aromatic carzene acid ester is, for example, a cardanate ester derived from an aromatic mono- or dicarboxylic acid having 7 to 12 carbon atoms and an alcohol having 1 to 12 carbon atoms. Specifically, when it comes to
Methyl benzoate, ethyl benzoate, methyl toluate,
Examples include ethyl toluate, ethyl anisate, phthalate, and diethyl.

2) Cal d7ff? Alternatively, acid chlorides of sulfonic acids are one of the preferred electron-donating compounds for use in the present invention. The carboxylic acid is a monocarzenic acid, a dicarzenic acid, or a sulfonic acid decide, and in this case, as the carnoic acid moiety, those mentioned above regarding the carunic acid ester are suitable.

In addition, as sulfonic acid, fats having about 1 to 12 carbon atoms are used.
17374 and aromatic monosulfonic acids are suitable. Specifically, acrylic acid, acetic acid, isophthalic acid, crotonic acid, monochloroacetic acid, trichloroacetic acid,
Phenylacetic acid, benzoic acid, cinnamon bark, Wl, F lumitic acid, myristic acid, 3-phenylpro2one, 2-furancarzic acid, propionic acid, butyric acid, n-hexonic acid,
Monocarzenic acid such as lauric acid, cical acid such as fumaric acid, maleic acid, conocarboxylic acid, marronic acid, cenocenic acid, etc.
Examples include chlorides, bromides and iodides of sulfonic acids such as chlorosulfonic acid, ethanesulfonic acid, benzenesulfonic acid and chlorosulfonic acid. In particular, saturated or unsaturated aliphatic monocarunic acids or polycardic acids having 1 to 10 carbon atoms,
Acid halides of aromatic carminic acids are preferred. Specific compounds include acrylic chloride, acrylic bromide, acetyl chloride, acetyl bromide, acetyl iodide, atonyl chloride, crotonyl bromide, trichloroacetyl chloride, trichloroacetyl bromide, benzoyl chloride, benzoyl bromide,
Examples include benzoyl iodide, cinnatyl chloride, 7malyl dichloride, malonyl dichloride, ethylsulfonyl chloride, ethylsulfonyl bromide, benzenesulfonyl chloride, benzenesulfonyl bromide, and the like.

3) Other electron-donating compounds In addition to the above-mentioned compounds, compounds that can be used as electron-donating compounds in the present invention include ethers, keto/, anne, thioethers, alcohols, and phosphorus compounds.

3 Component (C) Component (C) is a halogen-containing compound.

1) Titanium Compound There are various titanium compounds, but they usually have the general formula TI (
OR) 4-nXn (where R is a hydrocarbon residue having 1 to 1 carbon atoms, X represents a halogen, and n represents O<
Indicates the number n <, 4. )).

Specifically, TlC14, T I B r 4, T11
Titanium tetrahalides such as 4, 71 (OCH3
)C13,TI(OC2H5)C13,'rt(OC
4H9) C13, TS (OC2) I5) Br3,
trihalogenated alkoxytitanium, such as TI (OC2
H5) C12, TI (OC4H9)2C12, TI
(OC4Hg)2Br2, etc. Norihalogenated dialkoxytitanium, TI (OC2H5)3CI %Ti (
OC4Hg)3CI, TI (OIC3HB)3C
Examples include monohalogenated trialkoxytitanium such as 1-. Among these, titanium tetrahalide is preferred, and titanium tetrachloride is preferred.

Further, this titanium compound may be one obtained by completely reacting TiX4 (where X represents a halogen) with an electron-donating compound. As a specific example, TlC14"CH3COC2H5, TlCl4- CH
3C02C2T (5, TiC14-C) (3COCI
, T%c14@c6H5co2c2H5, TlC14
There are 5C6T (5NH2, etc.).

2) Silicon compound There are various silicon compounds, but usually -V formula R4-
n5IXn (where R is a hydrocarbon residue, X is a halogen,
Cram school is a number where 0<n and 4. ) can be mentioned. Specific examples include 81C14, 8iBr4,
CH3SiCl3, (C2f(5)2SIC12, etc.) Also, with the general formula 5i(OR)4-nXn (where R is a hydrocarbon residue, X is a halogen, and n represents the number of O<n>4). The compounds represented can also be exemplified. Specific examples include S t (OC2H5)C13, Si (OC4Hg
)2C12, etc. Among these compounds, silicon tetrachloride is preferred.

3) Other halogen-containing compounds Any halogen-containing compound can be used, but the following are representative examples.

ZnX2, BI3, AlX3, GaX3, Ge1X4.
5nX4, PX5, PX3.5bX5.5bX3, BI
X3.5eX4, T e X4, Fe X3, FeX2
, NlX2, zrX4, vx4, vx3, NbX5,
Halides such as MoX5, WX6 (where X is halogen), AlX2 (OR), AIX (OR)2, PX
4 (OR), PX3 (OR) 2, PX2 (OR), 5
bX4(OR), 5bX3(OR)2 (where X is a halogen, R is a residual hydrocarbon having about 1 to 10 carbon atoms), 5OX2, VQ
There are compounds such as X3 (where X is halogen).

Among these compounds, halogen compounds of aluminum and iron are preferred. These compounds can be used alone or in combination of two or more.
More preferable results can be obtained when used in combination with the halogen or interhalogen compound proposed in Japanese Patent No. 88.

Among these compounds 1), 2) and 3), it is preferable to use the titanium compound 1).

When using compounds 2) and (or) 3),
It is preferable to use it in combination with the titanium compound of 1).

4. Synthesis of the catalyst component of the present invention The catalyst component of the present invention is a contact product of components (A) to fc).

1) The amount of each component to be used is as long as the effect of the present invention is recognized.
Although it is arbitrary, it is generally preferably within the following range.

The amount of component (B) to be used is I
-10, preferably IXl0-2-l
is within the range of

Component (C) is used in a molar ratio of 1 x 10 to 1 to the magnesium dihalide constituting solid component (A).
00 (a) range (preferably within the range of 0.1 to 100).

2) Contact method The catalyst component of the present invention contains component (B) in the aforementioned solid component.
, component (C).

Generally, the contact may be carried out at a temperature range of -100°C to 200°C. The contact time is usually about 10 minutes to an additional hour.

It is preferable that the solid component A) and the component B) to (C) be brought into contact with each other under stirring.
The contact can also be brought into contact by mechanical crushing, etc. The order of contact can be arbitrary as long as the effects of the present invention are enhanced.

The contact between solid component (A) and components CB) to (C) can also be carried out in the presence of a dispersion medium. The dispersion medium at this time can be selected from those exemplified as those to be used when producing component (A).

5. Polymerization of α-olefins 1) Formation of catalyst The catalyst component of the present invention can be used in the polymerization of α-olefins in combination with an organometallic compound as a cocatalyst. Any of the known organometallic compounds of metals in the periodicity range 1-WTS can be used as cocatalysts. Particularly preferred are organic aluminum compounds.

Specific examples of organoaluminum compounds include general formula R3
3-nAIXn or R43-mAl(OR5), T
I (where R3, R4, and R5 may be the same or different hydrocarbon residues having 1 to 20 carbon atoms, or hydrogen, X is a halogen atom, and n and m are each O< n <'
2.0, m < 1. ). Specifically, there are the following compounds.

iii) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triethylaluminum, tridecylaluzunium, etc.; (b) diethylaluminiumuramonochloride, diimbutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. Examples of the alkylaluminium include dialkyl hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and alkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum butoxy P, and diethylaluminium phenoxide.

In addition to these organoaluminum compounds (a) to (c), other organometallic compounds such as R3-, AI(OR), (
Alkylaluminum alkoxyyt represented by 1<a<3, R7 and R8 are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different, can also be used in combination. For example, the combination of triethylaluminum and ethylaluminum ethoxide, the combination of diethylaluminum monochloride and diethylaluminum ethoxide, the combination of ethylaluminum dichloride and ethylaluminum ethoxide, the combination of triethylaluzinium and diethylaluminium chloride, It can be used in combination with diethylaluminum ethoxide.

There are no particular restrictions on the amount of these organometallic compounds used, but
0.5 to 10 in weight ratio to the solid catalyst component of the present invention
It is preferably within the range of 00.

In order to improve the stereoregularity of an α-olefin polymer having 3 or more carbon atoms, an electron-donating compound similar to that used in the preparation of the solid catalyst component such as ether, ester, or amine may be added and allowed to coexist during polymerization. is effective. The amount of the electron-donating compound used for this purpose is 0.001 to 2 mol, preferably 0.05 to 1 mol, per 1 mol of the organoaluminum compound.

2) α-Olefin The α-olefin polymerized with the catalyst system of the present invention has the general formula RCH=CH2 (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and a branched group may be contained). Specifically, 4L ethylene,
Propylene, butene-1, pentene-1, hexene-1
, 4-methylinten-1 and other olefins 1
%, preferred are ethylene and propylene.

In the case of the polymerization of these α-olefins, it is possible to carry out copolymerizations of ethylene with the above-mentioned α-olefins up to its I weightless cent, preferably weighted ordinary cent, and also of propylene and its Copolymerization with the above-mentioned alpha-olefins, especially ethylene, can be carried out up to a weighted standard.

Co-merization with other polymers (eg, vinyl acetate, diolefins) other than penta-olefins can also be carried out.

3) Polymerization The M medium system of the present invention is of course applicable to ordinary slurry polymerization, but it can also be used for continuous polymerization in liquid phase solvent polymerization, solution polymerization, or gas phase polymerization that does not substantially use a solvent. Whether it is batch polymerization or prepolymerization,
Applicable. As a polymerization solvent in the case of slurry polymerization,
Saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, intane, cyclohexane, chlorine, and toluene may be used alone or in mixtures. The polymerization temperature is from room temperature to about 200°C, preferably from 150°C to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time.

6. Experimental Examples Example-1 1) Synthesis of solid components Dehydrated and deoxidized N
- Introduce a milliliter of hebutane, then MgCl2
k O, 1 mol and TI(ORu) 4 t'' 0.
After 2 hours, lower the temperature to 40℃, then add 1 mouthful of Methyl High.
Quenpolysiloxa/(20 centistokes)
A total of 15 oriliter was introduced and allowed to react for 2 hours.

The generated solid component was washed with 1-hbutane and a portion was taken out for compositional analysis, and it was found that TI='13,2[1
萐-cent, MK-6, triple 1-nocent, CI = 1
It was 2.31 cents.

2) Preparation of catalyst component 25 liters of dehydrated and oxygenated 1-heptane was introduced into a flask which had been sufficiently flushed with nitrogen, and 0.03 mol of the solid component CA) synthesized above was introduced in terms of tMg atoms. n-hebutay5tJ<TlC140 in liter
,025 mol were mixed and introduced into the flask over 1 minute at 31°C, and reacted at 50''C for 2 hours.

After the reaction was completed, it was thoroughly washed with n-hebutane. Then n
-Hebutane 50<0.01 ethyl benzoate per liter
The moles were mixed and introduced into a flask at ℃, and the li
The reaction was carried out for 2 hours at O'c. After the reaction was completed, it was thoroughly washed with n-hebutane. Then 1,2-dichloroethane 50
<Mix 1450 ml of TLC to 1 liter and introduce into a flask at 30°C for 1 minute, then at 80°C for 2 minutes.
Allowed time to react. After the reaction was completed, it was thoroughly washed with n-hebutane. Next, 1,2-dichloroethane and TlC from the same author
Using 14t, same 4#! I reacted on the matter. After the reaction was completed, it was thoroughly washed with eebutane and used as a catalyst component.

When a portion was taken out and analyzed for composition, TI=3.
There were 0 layers of clothing and an armpit.

3) Equipped with propylene polymerization stirring and temperature control? After repeating the vacuum-propylene Ij exchange several times in a stainless steel autoclave with an internal volume of 1.51 J, 500 ml of thoroughly dehydrated and deoxidized n-heptane, 222 mg of triisobutylalonium, and sesquivalent Ethylaluminum chloride (up to) milligrams, methyl paratoluate (50 milligrams), and the catalyst component synthesized above were introduced in an amount equivalent to 0.4 R/IJ grams in terms of Tl atoms. Polymerization was carried out under the following conditions: '·, polymerization pressure = 6 Xll/x', polymerization temperature 10°C, and polymerization time 22 hours. After the polymerization was completed, the obtained polymer slurry was treated with ethanol, separated by filtration, and dried. 110 duram poly i- was obtained. The stereoregularity of this powder/li-r- (hereinafter referred to as product II) was 99.21 by boiling heptane extraction test. The bulk density (hereinafter referred to as polymer BD) is 0.36 (t/cc
), the polymerization activity is 229,000 (g
-polymer/g-Ti).

Example-2 1) Production of catalyst component In the production of the catalyst component of Example-1, 1,2 dichlorop
The production was carried out in exactly the same manner except that the amount of ethane used was 6 milliliters. Composition analysis revealed that the T1 content was 2,7611 cm, e-cent.

2) Polymerization of propylene Mixing was carried out under exactly the same conditions as in Example-1.

H2 grams of polymer was obtained.

Mixed activity (g-4 remer/tt-TI) 317
0.000 polymer B D = 0,342 (K
/ ”) Product II = Target, 6 (H) Example-3 1) Production of catalyst component (Production was carried out in the same manner. When the composition was analyzed, the content of T+1 was 1.90% by weight.

2) 1 cup of propylene Polymerization was carried out under exactly the same conditions as in Example-1.

133 grams of polymer was obtained.

Polymerization activity (g-polymer/g-Ti) = 277oo.

” Polymer B D = 0.355 (g/cc) Product I1. 9 (H) Example-4 1) @Production of catalyst component In the production of the catalyst component of Example-2, the first reacted cello TtC14f)Cb') K 5IC140,0
All were manufactured in the same manner except that 25% Af was used.

Compositional analysis revealed that the T1 content was 1.93% by weight.

2) Polymerization of propylene Polymerization was carried out under exactly the same conditions as in Example-1.

136 grams of polymer was obtained.

Polymerization activity (g-polymer/t<-TI) = 2
84.00 (1 poly-v-B D =0.375 (
K/C'-) Product II-, 2(-) Example-5 1) Production of solid component The same amount of the solid component produced in the same manner as in Example-1 was taken as in Example-1, and h-hebutane was added. It was introduced into the flask together with a little 2Si. 5 ml of xylene, 0.0 ml of ethyl benzoate. A mixture of 140,05 moles of 5IC and 140.05 moles of
The mixture was introduced into the flask over a period of 10 minutes, and reacted at 50'C for 2 hours. After the reaction was completed, it was washed with n-hebutane. Then add ml of xylene and TlCl450 f
Liter was mixed and introduced into the flask at 30'C for 1 minute, and reacted at 80'C for 1 hour. After the reaction is complete,
Remove the supernatant and add 3 ml of xylene and Tt.
Ct 450 ml of the mixture was introduced at I°C, and the temperature was increased to
The mixture was allowed to react for 2 hours. After the reaction was completed, it was thoroughly washed with n-hebutane and used as a catalyst component. When we analyzed the composition, T
The i content was 1.86 weight percent.

2) Polymerization of propylene The entire polymerization was carried out under exactly the same conditions as in Example-1.

268 grams of pirimer were obtained.

Polymerization activity (K-polymer/g-TI) = 555
,000 polymer B D = 0. ．． 40 (g/c
c) Product I1. = 18.0C%) Example-6 1) Production of catalyst component In the production of the catalyst component of Example-5, 5IC140.05 mol and 5l (OC2H5
) was prepared in exactly the same manner except that 40.01 mol was used.
I did it. Compositional analysis revealed that the Ti content was 1.63% by weight.

2) Polymerization of propylene Polymerization was carried out under exactly the same conditions as in Example-1.

188 grams of pirimer were obtained.

Polymerization (K-zelimer/g-rt) = 39
2,000 Polymer B D=0.39 (K/C'-)
Product 11=! Name, 8 (嗟) Example-7 1) Production of catalyst component Solid component produced in the same manner as Example-1 (for example-1)
The same amount was taken and introduced into the flask together with 25 liters of n-heptane. 10 ml of n-hebutane and 8
A mixture of 1C and 140,025 mmol of I at t- (capital) °C.
The mixture was introduced over a period of minutes and reacted at 50'C for 1 hour. After the reaction was completed, it was thoroughly washed with n-hebutane.

Next, 0.01 mol of ethyl benzoate was mixed with 1/2 milliliter of dichloroethane and introduced at 30'C. Then 1450 ml of TIC was introduced at 7°C. s
The reaction was allowed to take place at 0°C for 1' hour. After the reaction, remove the supernatant and add 1.2 ml of dichloromethane.
1450 liters of C was mixed, introduced at 0.degree. C., and reacted for 2 hours at 0.degree.

After the reaction was completed, it was thoroughly washed with n-hebutane to obtain a catalyst component. When we analyzed the composition, the T1 content was 1.761.
It was t/c-cents.

2) Polymerization of zolopyrene Polymerization was carried out under exactly the same conditions as in Example-1.

124 grams of polymer was obtained.

Polymerization activity (II--polymer/tr-TI) =
257,000 polymer s D = 0.34 (g/
cc) Product II=! θ, 0 (H) Example 8 1) Production of catalyst component A solid component produced in the same manner as in Example 1 was introduced into a flask together with 5 ml of n-heptane, which was the same as Example 1. A mixture of δ ml of xylene, 0.025 mol of benzoyl chloride, and 0.05 mol of C14 (
The mixture was introduced over a period of minutes at 100°C and allowed to react at 200°C for 2 hours. After the reaction was completed, it was thoroughly washed with n-hebutane.

Next, a mixed solution of 1,450 ml of xylene and 1,450 ml of TLC was added in portions at 30°C.

The reaction was allowed to proceed for 1 hour at an intercalary temperature. After the reaction was completed, the supernatant liquid was collected, and a mixed solution of xylene I milliliter and TIC14 (capital) milliliter was introduced at 1°C and reacted at 80'C for 2 hours. It was thoroughly washed with butane and used as a catalyst component. A compositional analysis of the longitudinal healing material revealed that the TI content was 1.58% by weight.

2) Polymerization pressure of propylene under the polymerization conditions of Example-1? Polymerization was carried out under exactly the same conditions except that 5-2 was used. 238
Grams/rimers were obtained.

Polymerization activity (g-po!jmer/g-TI) = 4
95,000 break −r −B D = 0.39 (g
/cc) Product II=Silver, 0 (嗟) Example-9 1) Production of catalyst component In the production of the catalyst component in Example-5, no changes were made except that the amount of 5Ic14 used was changed to 0.025 mol. Produced in the same manner. When we analyzed the composition, the T1 content was 2.23]
It was 1%.

2) Polymerization of propylene 5Ill! M? In the condition of 1i-1, except that the organoaluminum was changed from triinobutylaluminum to 125 mg of triethylaluminum, and the use of methyl radruylate was changed to 125 mg of triethylaluminum.
Polymerization was carried out under conditions such that all<IW1. 122 grams of polymer was obtained.

Polymerization activity (g-&rimer/g-'r amount) = 254,00
0 Polymer nD = 0.39 (g/cc) Product II = 97 (H) Example-10 1) Production of catalyst component The solid component produced in the same manner as in Example-1 was increased in the same amount as in Example-1. , and 25 liters of n-hebutane were introduced into the flask. n-hebutane 10ml K 5s
A mixed solution of 40.013 moles of Ct 'f was introduced in portions at 30°C and reacted at 1°C for 2 hours.

Thoroughly washed with n-hebutane. Then n-hebutane 1
A mixture of 0.025 mol of ethyl benzoate in 0 ml was added in portions at 1°C, and the mixture was reacted for 1 hour at intercalary°C. After the reaction was completed, it was thoroughly washed with n-hebutane. Next, 1450 ml of TIC was introduced over 1 minute at 50°C, and the reaction was allowed to proceed at 50°C for 1 hour. After the reaction was completed, the supernatant was removed, and then 1450 milliliters of TiC was added in portions at (1)°C, and the reaction was allowed to proceed at light°C for 2 hours. After the reaction was completed, it was thoroughly washed with hebutane and used as a catalyst component. When the composition was analyzed, the η content was 2.86 wt.
-It was cents.

2) Polymerization of ethylene In a stainless steel autoclave with an internal volume of 1.5 liters equipped with stirring and temperature control equipment, vacuum-ethylene pre-exchange was repeated several times, and n-hebutane 'fr800 which had been sufficiently dehydrated and deoxidized was placed. milliliter, 140 <ligrams of triinobutylaluminum, and tt corresponding to 0.14 milligrams of the catalyst component synthesized above were introduced. The temperature was raised to A℃, and the total hydrogen partial pressure was 4,51#/(-
Then, an ethylene solution was introduced to bring the total pressure to 9:41. Polymerization was carried out for 3 hours. These reaction conditions were kept the same during the polymerization.

However, the pressure, which decreased as the polymerization progressed, was kept constant by introducing only ethylene. 1
35 grams of polymer was obtained.

Polymerization activity (g-polymer/g-Tl) = 96
4,000 poly f-B D=0.42 (g/cc) Example-11 1) Production of solid component The solid component produced in the same manner as in Example-1 was taken in the same scale as in Example-1, and n- It was introduced into the flask along with 6 milliliters of hebutane. Mixture of xylene 25 liters, ethyl benzoate o, oos moles, 5tC140.05 moles i
Introduced into the flask at 30°C for 1 minute, then at 50°C for 2 minutes.
Allowed time to react. After the reaction was completed, it was thoroughly washed with n-hebutane. Next, add ml of xylene and TiC1
450 ml of the mixture was mixed and added to the flask at 30'C, followed by reaction at 30'C for 1 hour. After the reaction was completed, the supernatant liquid was taken out, and a mixed solution of 1 ml of xylene and 1450 ml of TiC was introduced at 80° C. and reacted at 80° C. for 1 hour. After the reaction is complete, remove the supernatant and add ml of xylene and TLC1450.
A milliliter of mixed g was introduced at 130'C and reacted for 1 hour at an intercalary °C. After the reaction was completed, it was thoroughly washed with n-hebutane and used as a catalyst component. When I analyzed the composition, it was found that T1
The content was 3.35 cents.

2) Polymerization of propylene Polymerization was carried out under exactly the same conditions as in Example-8.

298 grams of I remer was obtained.

Polymerization activity (g-Po!Jmer/*-Ti) = 6
20,0n (1 poly, r-BD=0.37 (+r/c
c) Product II = shame, 2 (%) Applicant's agent Kiyoshi Inomata

Claims (1)

[Scope of Claims] A catalyst component for olefin polymerization, which is a contact product of the following components (A) to (C). Component (A) A solid composition composed of magnesium dihalide, titanium tetraalkoxide, and a polymeric silicon compound having a structure represented by -5t-O- (where R is a hydrocarbon residue). Component B) Electron-donating compound component (C) Halogen-containing compound