JPS62236805A - Catalyst component for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the titled inexpensive catalyst component which can give a polymer of excellent stereoregularity in high activity, comprising a product of contact between a specified solid Ziegler catalyst component and a phosphorus halide compound. CONSTITUTION:A solid Ziegler catalyst component (A) is obtained by contacting 1X10<-3>-1,000mol of a titanium compound (a) having at least one OR<2> group of formula I (wherein R<2> is a hydrocarbon residue, X is a halogen and 0<=n<=3) with 1mol of a Mg compound (b) such as MgCl2 and 1X10<-3>-100mol of an electron-donating compound (c) (e.g., diheptyl phthalate) by grinding in, e.g., a rotary ball mill. The titled catalyst component is obtained by placing component A and a phosphorus halide compound (B) of formula II or III (wherein R<8-11> are each a 1-10C hydrocarbon reside, a+b+c=3 or 5, 0<a<=5, 0<=b, c<5, d+e+f=3, 0<d<=3, 0<=e and f<3) at a P to Ti atomic ratio of 1X10<-3>-100 in, e.g., a rotary ball mill and contacting them together in the presence of an inert diluent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] Technical Field The present invention relates to a catalyst component 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 dialkylmagnesium and organoaluminum are used as carriers for transition metal compounds such as titanium compounds, highly active catalysts can be obtained. It is known that many inventions have been proposed.

Although these prior art techniques have a certain degree of catalytic activity, the properties of the resulting polymers are not sufficient and improvements are desired. Polymer properties are extremely important in slurry polymerization, gas phase polymerization, and the like. This is because if the polymer properties are poor, polymer adhesion within the polymerization tank and other problems may occur.

In such a method, it is common to use a large amount of a titanium halide compound (particularly titanium tetrachloride) as a transition metal compound such as titanium to contain the titanium compound in the catalyst component. The basic unit is bad. This is extremely disadvantageous for producing catalysts. Many of the titanium halogen compounds that were not included in the catalyst component need to be removed from the catalyst component, which requires a large amount of solvent, etc., which increases the manufacturing cost of the catalyst and also makes it unnecessary. Titanium halogen compounds need to be decomposed, but this often generates halogen gas, hydrogen halide, etc., which is extremely bad for environmental health.Therefore, we are working to improve the basic unit of titanium halogen compounds. It is desired to do so.

By the way, as a prior art similar to the present invention (details will be described later), there can be mentioned the one described in Japanese Patent Application Laid-open No. 104303/1983. According to this known technique, it is said that by using a phosphorus compound, the stereoregularity does not change even when the molecule ffl (MFR) of the produced polymer changes. However, as far as the present inventors know, this known technique seems to have the following two problems.

(a) The stereoregularity of the produced polymer is insufficient, and the isotafticity is only about 94%.

(b) A large amount of titanium halide (T t
Cl4) is used.

[Summary of the invention]

(2) The purpose of the present invention is to provide a solution to the above-mentioned problems, and to achieve the above-mentioned objects by using a catalyst component made of specific components.

That is, the catalyst component for olefin polymerization according to the present invention is
It is characterized by consisting of a contact product of the following components (A> and (B)).

Component (A) A Ziegler-type catalyst solid component containing as essential components a titanium compound having at least one OR group (wherein R1 represents a hydrocarbon residue), magnesium, halogen, and an electron-donating compound.

“I’m angry” Phosphorous halogen compounds.

When olefins are polymerized using the solid catalyst component according to the present invention as the transition metal component of a Daegler catalyst, a polymer with high activity and good stereoregularity can be obtained.

Also, unexpectedly, polymers with higher stereoregularity are obtained than when using halogenated titanium compounds such as titanium tetrachloride. The reason why polymers with such high stereoregularity are obtained is still unclear. Polymers with high stereoregularity are important for widening the applications of polymers.

And in order not to use halogenated titanium compounds,
It becomes unnecessary to process the halogenated titanium compound during catalyst production, and the production cost can be greatly reduced, which is extremely advantageous in industrial production.

(Detailed Description of the Invention) Catalyst component and its production The catalyst component of the present invention is produced by contacting components (A) to (B).

Component (A) Component (A) of the present invention comprises (a) at least one OR
A titanium compound having one group, (b) magnesium, (c) halogen, and (d) an electron-donating compound as essential components, and which satisfies these conditions and can be used as a solid component of a Ziegler type catalyst. Any material can be used as long as it is urea.

Here, to consider (a) to (d) as essential components means that components (a) to (d) must first be used in their original form as component (A).
>It does not mean that it exists inside. Therefore,
Components (b) and (c) representing elements do not need to be considered in terms of their existence form in component (A), but components (a) and (d), which are compounds, are present in component (A). It may be possible that it reacts with other components and exists as a separate compound.

Therefore, components (a) and (c) refer to raw materials for producing component (A). ). And the component (A) of the present invention
In addition to these, as long as it contains components (a) to (d),
During its preparation, it is also possible to use other components such as silicon, aluminum, boron, etc., and it is also possible for these to remain in component (A). This is why component (A>) is defined as having (a) to (d) as essential components.

Component (A) can be produced by any suitable method. Specific examples of suitable manufacturing methods are as follows.

(1) Production method (i) A method of bringing a magnesium halide, an OR1 group-containing titanium compound, and an electron-donating compound into contact.

(ii) Alkoxy-containing magnesium compound and 0R
A method of bringing a 11-containing titanium compound, an electron-donating compound, and a halogen source compound into contact when the above-mentioned compound does not have a halogen.

(iii) A method of contacting an electron donor and a silicon halogen compound with a solid component obtained by contacting a magnesium halide, a titanium tetraalkoxide, and a specific polymeric silicon compound.

(iv) A method in which a magnesium compound (preferably a halogen compound) is dissolved in titanium tetraalkoxide and an electron donor, and then precipitated.

These production methods are well known for producing Ziegler-type solid catalyst components. The following documents can be cited as those that disclose these manufacturing methods. JP 52-36913, JP 54-40293, JP 58-32605, JP 58-183709, l1i
159” 149905, various publications, etc.

Among these, (i) and (iv) are preferred.

(2) Raw material (I) An example of a titanium compound used to produce component (A) is a compound represented by the following formula.

Ti(OR)
n hydrogen chloride residue, preferably one having about 1 to 10 carbon atoms, X represents a halogen, and n represents a number of 0≦n≦3)
.

Specific examples include T i (OC2H5)4, T i
(0-i C3H7) 4, Ti (Onc4Hg) 4, Ti (Onc6H13) 4, Ti (0-nc3H7) 4, T + (0-i C4H9) 4, Ti (0-nCBHl 7) 4 , Ti(OCH2CH(C2H5〉04H9)4, Ti
OC2H5) 3C1, Ti(OC2To1, ) 2 C12, Ti(On
C4Hg)3CI, T i (0-nc:4l-19) 2Cl 2, T
+ (OC2H5) 3Br.

Examples include Ti(OC6H13)C13, Ti(0-nCBHl7)2CI2, and the like.

Moreover, the titanium compound for component (A) may be a condensate of the above-mentioned compounds. Examples include compounds represented by the following formula.

(It is a hydrocarbon residue having about 1 to 10 carbon atoms, which may be the same or different, and n indicates a number from about 2 to 10.) Specific examples of such condensates include isopropoxide with n=2 , n=4, and n=10, and n=2, n=4, n=7, and n=10 polymers of normal butoxide.

(b) Magnesium compounds used to produce component (A) include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylates. etc. can be mentioned.

The halogens in "halide" in these compounds are chlorine,
Among these, chlorine is suitable. "Alkyl" or "alkoxy" is an aliphatic group having about 1 to 10 carbon atoms or phenyl (therefore, "alkyl" or "alkoxy" includes "phenyl" or "phenoxy"). The "carboxylic acid" is suitably a monobasic acid having about 2 to 20 carbon atoms.

Particularly preferred among these are magnesium halides, especially magnesium chloride.

(c) Halogen A typical example of the halogen source compound is magnesium halide, which also serves as a magnesium source.

Other specific examples include silicon halogen compounds, aluminum halogen compounds, tin halogen compounds,
Examples include metal halogen compounds such as zinc halogen compounds, chlorine, hydrogen chloride, etc.

(d) Electron donors that can be used in the production of solid component (A) include alcohols, phenols, carbons,
Oxygen-containing electron donors such as aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles,
Examples include nitrogen-containing electron donors such as isocyanates.

More specifically, (a) methanol, ethanol, propatool, butanol, pentanol, hexanol,
Alcohols with 1 to 18 carbon atoms such as octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, (b) phenol, cresol, xylenol, ethylphenol, propylphenol, cumyl 6 carbon atoms that may have an alkyl group such as phenol, nonylphenol, naphthol, etc.
phenols having 3 to 25 carbon atoms, (c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde; Aldehydes with 2 to 15 carbon atoms such as naphthaldehyde, methyl formate, methyl acetate, 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, benzoic acid methyl,
Ethyl benzoate, propyl benzoate, butyl benzoate,
Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, C2 to C20 acid esters such as dibutyl phthalate, dihebutyl phthalate, γ-butyrolactone, γ-valerolactone, coumarin, phthalide, ethylene carbonate, ethyl silicate, butyl silicate, phenyl trisilicate, Am2-free esters such as silicate esters such as ethoxysilane; acid halides having 2 to 15 carbon atoms such as (t)acetyl chloride, benzoyl chloride, toluic acid chloride, anisyl chloride, phthaloyl chloride, iso-phthaloyl chloride; <
H) Ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, and diphenyl ether; (S) Acetamides such as acetic acid amide, benzoic acid amide, toluic acid amide, etc. , (l) Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, (l) Nitriles such as acetonitrile, benzonitrile, tolnitrile, etc. can be mentioned. Two or more types of these electron donors can be used.

(e) Optional components If necessary, other components may be included as optional components. Compounds used for such purposes include, for example, silicon halides such as 3iCl
Lower alkylhalosilanes 4ゝFor example, CH5iCl Silicon compounds such as alkylhydrodiene polysiloxanes, aluminum halides such as AlCl Lower alkoxyaluminum halides such as AI(OC2H5)2C1, lower alkoxyaluminums such as A I (OC2H5)3, A I (Oi
C38B)3, similar aluminum compounds, lower alkoxyborons such as B(OCH3)3, B(OC2H5)3, B(OnC4
Examples include boron compounds such as H9)3.

Preferred among these are silicon compounds, particularly alkylhydrodiene polysiloxanes having a structural unit represented by the following formula.

5i-0- Here, R7 has about 1 to 10 carbon atoms, especially about 1 to 6 carbon atoms,
is a hydrocarbon residue. This polymeric silicon compound is
It is preferable that the viscosity is about 0.1 to 100 centistics.

Specific examples of polymeric silicon compounds having such structural units include methylhydrodiene polysiloxane,
Ethylhydrodiene polysiloxane, 1.3.5.7
-titramethylcyclotetrasiloxane, 1.3.5,
7.9-pentamethylcyclopentasiloxane, etc.

(3) The amount of each component constituting the northernmost component (A) may be arbitrary as long as the effects of the present invention are observed, but it is generally preferred to be within the following range. The amount of titanium compound used is 1X10' to 100 in molar ratio to magnesium compound.
within the range of 0, preferably within the range of 0.01 to 10,
The amount of the electron donating compound to be used is within the range of 1.times.10@-3 to 100, preferably within the range of 0.01 to 10, in molar ratio to the magnesium compound. The amount of halogen used is within the range of 1 to 100, preferably 2 to 50, relative to magnesium in component (A). The amount of optional components to be used is arbitrary as long as the effects of the present invention are not impaired and the effects of their use are recognized, but in the case of typical methylhydrodiene polysiloxane, the molar ratio to the above magnesium compound is IX is within the range of 10' to 100, preferably within the range of 0.1 to 10,
More preferably, it is within the range of 1 to 5.

Component (B) Component (B) is a phosphorus halogen compound. Generally, compounds represented by the following formula are used.

PX8Rb(OR). Or here, x is halogen, R8, R9, R10 and R1
1 represents a hydrocarbon residue having about 1 to 10 carbon atoms, a+C=3 or 5, O<a≦5.0≦b<5.0
≦C<5, d+e+f=3, O<d≦3.0≦e<3.
0≦f<3.

Specific examples of compounds represented by the former formula include (a)
PCI PCl, PBr PBr5.3
・ Phosphorus halides such as 5. 3., (b)P(C2H5)2C1, P (CH)CI P (C6H5)2CI, 3
2ゝP(n-C4Hg)Br2, etc., alkyl phosphorus halides, (c)P(OCH3)C12, P(oCH)CI P(OCH3)2C1,252・P(0-nC4Hg)CI2, P( Examples of compounds represented by the latter formula include (d) phosphorus oxyhalides such as POCl2, POBr3, and (v) PO(C2H5)C12, PO. Oxyalkyl phosphorus halides such as (CH)CI2, (to)PO(OCH3)C12, PO(OCH)CI
There are oxydialkoxyphosphorus halides such as 2nd class. Among these, preferred are PCI P, CI P
OCl3.3ゝ 51 PBr P(OCH3) C12, 3ゝP (C2H5) CI 2. , etc., and more preferred are PCI, PCI and POCl3.

Contact of Component (A) and Component (B) The catalyst component for olefin polymerization according to the present invention is a contact product of the components (A) and (B) described above.

The contact conditions between component (A) and component <8) may be arbitrary as long as the effects of the present invention are observed, but the following conditions are generally preferred. Contact humidity is -50℃~200℃
The temperature is about 0.degree. C., preferably 0.degree. C. to 100.degree. Contact methods include rotary ball mill, vibration mill, JETSU I-mill,
Examples include a mechanical method using a media stirring pulverizer, and a method in which contact is avoided by stirring in the presence of an inert diluent.

Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, hexahydrocarbons, polysiloxanes, and the like. It is desirable that the atmosphere during the contact be made of an inert gas.

The quantitative ratio of component (A) and component (B) is within the range of 1 x 10-3 to 100 as the atomic ratio of phosphorus in component (B) to the titanium component constituting component (A> (phosphorus/titanium)). , preferably within the range of 0.1 to 10.

Formation of Olefin Polymerization Catalysts The catalyst components of the present invention can be used in the olefin polymerization in combination with an organometallic compound as a cocatalyst. Any organometallic compound of a metal of Groups 1 to 1 of the periodic table, which is known as a cocatalyst, can be used. Particularly preferred are organic aluminum compounds.

Specific examples of organoaluminum compounds include those represented by the following formula.

are hydrocarbon residues having about 1 to 20 carbon atoms or hydrogen, which may be the same or different, R14 is a hydrocarbon residue having about 1 to 20 carbon atoms, X is halogen, and n and m are each O≦n
<2, O≦m≦1. ) Specific examples include (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum,
Trialkylaluminum such as trioctylaluminum, tridecylaluminum, (b) alkylaluminum halide such as diethylaluminum monochlorite, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) diethylaluminum hydride , dialkyl aluminum hydride such as diisobutyl aluminum hydride, (d) alkyl aluminum alkoxide such as diethylaluminum ethoxide, diethylaluminium butoxide, diethylaluminium phenoxide, and the like.

These organoaluminum compounds (a) to (c) may be replaced with other organometallic compounds, for example, and R16 has 1 to 2 carbon atoms, which may be the same or different.
There are about 0 hydrocarbon residues. ) can also be used in combination with an alkyl aluminum alkoxide. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminium ethoxide, a combination of ethylaluminum dichloride and ethylaluminum jetoxide, a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminium chloride, Can be used in combination with

There are no particular restrictions on the amount of these organometallic compounds used, but
0.5 to 100 in weight ratio to the solid catalyst component of the present invention
It is preferably within the range of 0.

In order to improve the stereoregularity of an olefin polymer having 3 or more carbon atoms, it is effective to add and coexist an electron-donating compound such as an ether, ester, amine, or silane compound during polymerization. The amount of the electron-donating compound used for this purpose is 0 per mole of the organoaluminum compound.
．． 0.001 to 2 mol, preferably 0.01 to 1 mol.

Among the electron-donating compounds used as this so-called "external donor", preferred are piperidine, (, -OR group-containing compound, and S 1-OR group-containing compound. Specifically, 2.2. 6.6. Tetrameolefin The olefin polymerized with the catalyst system of the present invention has the formula R-CH=
It is represented by CH2 (here, R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and may have a branched group).

Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, and hexene-1,4-methylpentene-1. In these polymerizations, it is possible to carry out copolymerizations with up to 50% by weight, preferably 20% by weight, based on ethylene, of the abovementioned olefins, and up to 30% by weight, in particular with ethylene, based on propylene. can be copolymerized. Copolymerization with other copolymerizable monomers (eg vinyl acetate, diolefins) can also be carried out.

Polymerization The catalyst system of the present invention is applicable not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization in which substantially no solvent is used. It is also applicable to continuous polymerization, batch polymerization, or prepolymerization methods. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. 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.

Friend-Mouse-3 Example-1 - Thoroughly dried and nitrogen-substituted 0.4 liter volume.
Put 40 stainless steel balls of 12mmφ in a ball mill.
20 grams of MgCl2, 6.5 milliliters of diheptyl phthalate, Ti(OBu)2C12
5.0 grams of each were introduced, and 4.
Grind for 8 hours. After the pulverization was completed, the mixed pulverized product was taken out from the mill in a dry box and used as component (A').

Contact between component (A> and component (B)) 50 milliliters of sufficiently purified n-hebutane is introduced into a flask that has been sufficiently purged with nitrogen, and 5 grams of component (A) produced above and component <B) are introduced. 1 gram of PCl5 was introduced into each sample, and the mixture was kept in contact at 100° C. for 6 hours. After the contact was completed, it was washed with n-hebutane to obtain a catalyst component.

When a portion of it was taken out and analyzed, the titanium content of the catalyst component was 1.43% by weight.

In a 1.5 liter stainless steel autoclave equipped with stirring and temperature control equipment, 500 ml of thoroughly dehydrated and deoxygenated n-hebutane, 125 mg of triethylaluminum, and diphenyldimethoxy were added. 53.6 milligrams of silane and 15 milligrams of the catalyst component synthesized above were introduced. Then add H2 to 60
milliliter was introduced, the temperature and pressure were increased, and the polymerization pressure was 9/9 to 5.
Polymerization was carried out under the following conditions: cm G, polymerization temperature = 75°C, and polymerization time = 2 hours. After the polymerization was completed, the obtained polymer slurry was washed with water to separate the polymer and dried.

79.4 grams of polymer was obtained. On the other hand, from the boiling hebutane extraction test, 0.86 grams of polymer was obtained from the filtrate, all products 1. I (hereinafter abbreviated as T-1, I)
was 94.3 weight percent. VFR=7.6
(g/10 min), polymer bulk specific gravity -0.41 (g/c
c).

Example-2 Synthesis of component (A) Dehydrated and deoxygenated n
- 200 ml of hebutane is introduced, then MgC
Introducing 0.1 mol of l2 and 0.2 mol of T i (OnC4Hg)4, 95
The reaction was carried out at ℃ for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 12 ml of methylhydropolysiloxane (20 centistokes) 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-hebutane purified in the same manner as above was introduced into a flask that had been sufficiently purged with nitrogen.
0.03 mol of the solid component synthesized above was introduced in terms of MO atoms. Next, add 5 ml to 25 ml of n-hebutane.
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 3 hours. After the reaction was completed, it was washed with n-heptane. Next, 0.003 mol of phthaloyl chloride was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 70°C for 30 minutes.
The reaction was carried out at ℃ for 1 hour. After the reaction was completed, it was washed with n-hebutane (synthesis of component A). Then, 50.5 grams of PCI was introduced and reacted at 100° C. for 6 hours. After the reaction was completed, it was washed with n-hebutane.

The titanium content in the resulting catalyst component was 0.99 weight percent.

Polymerization of Propylene Polymerization was carried out under exactly the same conditions as in Example 1, except that the amount of diphenyldimethoxysilane used was 26.8 milligrams.

226 grams of polymer were obtained, MFR =.

4.3 (g/10 min), T-1,I = 99.0 weight percent, polymer bulk specific gravity -o, 47 (g/CC).

A ball mill purified in the same manner as in Example-1 was filled with balls in the same manner as in Example-1, and 12 grams of Mq(OC2H5)CI, 3.1 milliliters of phthalic acid chloride, and 3.7 grams of Ti(OBu)C13 were each added. The mixture was introduced and ground for 80 hours in a two-rotation ball mill. After grinding,
Take out the mixed pulverized material from the mill in the dry box,
It was designated as component (A).

Contact between component (A) and component (8) 50 milliliters of sufficiently purified n-hebutane was introduced into a flask that had been purged with nitrogen, and 5 grams of component (A) produced above were added as component (B). One gram each of PCI was introduced and allowed to contact at 100° C. for 3 hours.

After the contact was completed, it was washed with n-heptane to obtain a catalyst component. The titanium content of the catalyst component was 1.68 centimeters.

2-blade eLt>(lsu) In the polymerization conditions of Example-1, phenyltriethoxysilane 52 was used instead of diphenyldimethoxysilane.
Polymerization was carried out in exactly the same manner except that milligrams were used.

68.5 grams of polymer was obtained, MFR=4.6
(g/10 min), T-1, I = 95.8 weight percent, VFR = 7.8 (g/10 min), polymer bulk specific gravity -
0,37 (9/CC) Tea Tsuta.

Example-4 In the production of component (A>) of Example-2, except that diethyl phthalate was used instead of phthalic acid chloride,
Production was carried out under exactly the same conditions, and PO was used as component (B).
The catalyst was prepared in exactly the same manner except that 7 grams of CIO was used.

Polymerization of propylene was also carried out under exactly the same conditions as in Example-2. 132 grams of polymer was obtained, VFR=7.
1 (g/10 min), T-1,I = 98.6 weight percent, polymer bulk specific gravity -0.45 (y/cc).

Example 5 A catalyst component was produced in exactly the same manner as in Example 2, except that 0.004 mol of ethyl benzoate was used instead of phthaloyl chloride. Further, in the polymerization of propylene in Example 2, polymerization was carried out under exactly the same conditions except that 21.7 milligrams of phenyltrimethoxysilane was used instead of diphenyldimethoxysilane. 81.4 grams of polymer were obtained, MFR = 7.8 (g/10 min), T-1,l-
95,'1 weight percent, polymer bulk specific gravity = 0.4.
2 (y/cc).

Examples-6 to 8 In the production of the catalyst component of Example-2, P of component (B)
The catalyst components were produced in exactly the same manner except that the amount of Cl3 used was changed as shown in Table 1. Polymerization of propylene was also carried out in exactly the same manner.

The results are shown in Table-1.

-31 Example-9 to 10 In producing the catalyst component of Example-2, the catalyst component was produced in exactly the same manner except that the phosphorus compound shown in Table-2 was used instead of PC'+5, and the catalyst component was produced in the same manner as in Example-2. Polymerization was carried out in exactly the same manner.

The obtained results were as shown in Table-2.

Examples-11 to 13 Exactly the same except that the compounds shown in Table-3 were used in place of dihebutyl phthalate and Ti(OB u ) 2 Cl 2 in the production of component (A) in Example-1. The polymerization of propylene was carried out in exactly the same manner. The results are shown in Table-3.

- 36 Example-14 N- purified by thorough degassing in a flask that was sufficiently purged with nitrogen.
Add 100ml of hebutane, then MqCI
0.05 mol of 2, 0.1 mol of Ti(0-nCH), and nC
When 0.2 mol of 4H90H was introduced and stirred at 90°C for 2 hours, it completely dissolved and became a homogeneous solution. The temperature was lowered to 70° C., 0.3 mol of S i Cl 4 was introduced, and the mixture was stirred for 2 hours.

A solid component was precipitated, and the solid component was thoroughly washed with heptane. Next, 0.006 mol of phthaloyl chloride was introduced at 70° C. and reacted for 2 hours. After the reaction is complete, n
- Washed thoroughly with hebutane and used as component (A).

50 ml of purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen to contact A and (B).
4 grams of PCl5 and 0.6 grams of PCl5 were introduced, and they were brought into contact at 100° C. for 6 hours. After the contact was completed, it was washed with n-hebutane to obtain a catalyst component. The titanium content of the catalyst component was 1.71 weight percent.

Polymerization of propylene was carried out under exactly the same conditions as in Example 1. 138 grams of polymer were obtained, T-1,1=9
7.1 weight percent and MFR=5.3 (g/
10 minutes), and the bulk specific gravity of the polymer was 0.39 (g/CC).

Claims (1)

[Scope of Claims] A catalyst component for olefin polymerization, characterized by comprising a contact product of the following components (A) and (B). Component (A) A Ziegler-type catalyst solid containing as essential components a titanium compound having at least one OR^1 group (where R^1 represents a hydrocarbon residue), magnesium, halogen, and an electron-donating compound. component. Component (B) Phosphorus halogen compound.