JPS6334166B2 - - Google Patents

Description

[Detailed description of the invention]

[] Background of the Invention The present invention relates to a transition metal component of a so-called Ziegler type catalyst. From another point of view, the present invention relates to a method for producing this transition metal component. According to the present invention, a highly active solid catalyst for olefin polymerization can be obtained. Olefin polymerization catalysts, generally known as Ziegler-type catalysts, are a combination of a transition metal component and a reducing organometallic component. However, for example, the combination of titanium trichloride and diethylaluminum chloride does not necessarily have a sufficiently high catalytic activity, resulting in a large amount of catalyst residue in the produced olefin polymer, and therefore the product polymer is stable against heat and oxidation. In order to improve properties, complicated purification processes such as catalytic decomposition with alcohol and neutralization with alkali are required. For these reasons, highly active catalysts are desired, but improvement in catalytic activity seems to be primarily aimed at improving the transition metal component, and one such improvement is a catalyst using a magnesium compound as a carrier. There is. However, although catalysts with transition metal components such as titanium trichloride and titanium tetrachloride supported by magnesium compounds were meaningful in terms of their high activity per transition metal, the activity per support was still insufficient. There are many. It is preferable that the catalyst activity is not only high per transition metal but also high per support. In addition, one of the major drawbacks of such supported catalysts is that it is necessary to use a large excess of the transition metal compound component relative to the support during the catalyst activation stage, and as a result, unreacted transition metal compound components In some cases, the components required cleaning, decomposition, etc. This operation is extremely disadvantageous in terms of industrial production of the catalyst component, and the so-called "unit consumption" of the catalyst component is not good, leading to an increase in catalyst production costs. [] SUMMARY OF THE INVENTION The present invention aims to provide a solution to the above-mentioned problems, and attempts to achieve this object by means of a supported transition metal catalyst component prepared in a specific manner. Therefore, the catalyst component for olefin polymerization according to the present invention is a contact product of the following components (1) to (4);
It is characterized by: Component (1) At least one compound selected from the group consisting of the following magnesium compounds (a) to (f), or a mixture thereof, (a) magnesium dihalide, (b) halohydrocarbyloxymagnesium, (c) Magnesium dialkholate, (d) Organic acid salt of magnesium, (e) Mg(OH ₂ ), MgO, MgCO ₃ or
MgSO ₄ , (f) Magnesium and aluminum double oxide or magnesium and silicon double oxide, (2) Titanium alkoxy group-containing compound, (3) Polymer silicon compound having a structure represented by the following general formula (However, R ¹ represents a hydrocarbon residue.) (4) Liquid halogen compound of titanium or vanadium (However, component (2) and component (4) are not the same). According to one embodiment of the present invention, the olefin polymerization catalyst component according to the present invention is a contact product of the above four essential components and optional component (5). (5) Electron-donating compounds. Effects When α-olefin is polymerized using the solid catalyst component according to the present invention as a transition metal component of a Ziegler catalyst, both the amount of polymer produced per transition metal and the amount of polymer produced per carrier are high. Although it is not necessarily clear why the catalyst component of the present invention provides a Ziegler catalyst with such high activity per transition metal and per support, it is possible to obtain a Ziegler catalyst with high activity per transition metal and support. It cannot become an active catalyst. Therefore, it is presumed that the four constituent components (or five components depending on essentiality) interact in a complex manner, resulting in a highly active catalyst component. When component (5) is used, the effect of making the catalyst component even more highly active can be obtained. Further, one of the major advantages of the present invention is that the cost of manufacturing the catalyst is lower than that of conventional supported catalysts. As mentioned above, conventional supported catalysts have very poor so-called "unit consumption", resulting in a significant increase in cost. Particularly in many cases, since the transition metal component is used in large excess with respect to the carrier, it is necessary to wash the transition metal component, and it is also necessary to treat the unreacted transition metal. Therefore, when considering industrial production of catalysts, large equipment is required in addition to the catalyst synthesis section, which causes an increase in costs. Further, in the cleaning operation of the transition metal component, there is a possibility that the catalyst may be deactivated, which is very inconvenient. Depending on the manufacturing method, the solid catalyst component of the present invention has a very good transition metal component consumption rate, so cleaning of unreacted transition metal components after catalyst component synthesis is almost unnecessary (in many cases unnecessary), and industrial production is possible. This is extremely advantageous. Such effects of the present invention are achieved by the above-mentioned essential 4
It is brought about by the combination of ingredients,
In particular, a liquid titanium or vanadium halide compound, especially titanium tetrachloride, is added to a magnesium compound carrier, especially magnesium chloride, in the presence of a titanium alkoxide (component (2)) and a hydrogen polysiloxane (component (3)). This is thought to be mainly due to the fact that it is supported. In this case, it is important that the polysiloxane is a hydrogen polysiloxane (see Example 3 and Comparative Example 3 below). [] Detailed Description of the Invention The catalyst component according to the present invention comprises the following essential components (1) to
It consists of a contact product of (4) and optional component (5). 1 Component (1) Component (1) is at least one compound selected from the group consisting of the following magnesium compounds (a) to (f) or a mixture thereof. (a) Magnesium dihalide For example, MgF ₂ , MgCl ₂ , MgBr ₂ , MgI ₂ ,
and so on. (b) Halohydrocarbyloxymagnesium For example, Mg(OC ₂ H ₅ )Cl, Mg(OC ₆ H ₅ )ClMg
(OH)Cl etc. (c) Magnesium dialkholate For example, Mg(OC ₂ H ₅ ) ₂ , Mg(OC ₄ H ₉ ) ₂ ,
Examples include Mg( _{OC6H5 )2 .} (d) Organic acid salts of magnesium, such as Mg (OCOCH ₃ ) ₂ , Mg
(OCOC ₁₇ H ₃₅ ) ₂ Mg (OCOC ₆ H ₅ ), and others. (E) Mg(OH) ₂ , MgO, MgCO ₃ , and MgSO ₄ (F) Double oxide of magnesium and aluminum, double oxide of magnesium and silicon. As a mixture of components (a) to (f), for example,
Mixture of _MgCl2 and Mg _{( OC2H5} ) ₂ , _MgCl2 and Mg
There are mixtures with (OH) ₂ , etc. Of course, among the above magnesium compounds, those having water of crystallization can also be used. Among these compounds, magnesium dihalide is particularly preferred. 2 Component (2) Titanium alkoxy group-containing compounds are not only simple alkoxides in which the valence of titanium is filled only with alkoxide groups, but also compounds in which a part of the valence is filled with other groups such as halogen groups. Compounds containing alkoxide groups are also included. Specific examples include Ti(OC ₂ H ₅ ) ₄ , Ti(OC ₃ H ₇ ) ₄ , Ti(O-
_nC4H9 ) ₄ , Ti _{( OC6H5} ) ₄ , Ti _{( O} - _nC4H9 ) _3Br ,
Examples include Ti(O-nC ₄ H ₉ ) ₂ CI ₂ , Ti(O-nC ₂ H ₅ ) ₂ Br ₂ , and so on. Among these metal alkoxy group-containing compounds, tetraalkoxytitanium is particularly preferred. 3 Component (3) General formula

Specific examples of polymeric silicon compounds having the structural unit represented by the formula (R ¹ represents a hydrocarbon residue) include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, and cyclohexyl. Examples include hydropolysiloxane. The degree of polymerization of these polymer silicon compounds is not particularly limited, but in consideration of handling, it is preferably about 10 centistokes to 100 centistokes. Although the terminal structure of these hydropolysiloxanes does not significantly affect the catalyst component of the present invention, it is desirable that the terminal structure is capped with an inert group such as a trialkylsilyl group. Among these polymeric silicon compounds, alkylhydrodiene polysiloxanes, particularly methylhydrodiene polysiloxanes, are preferred. 4 Component (4) A liquid titanium halogen compound or vanadium compound (excluding the same compound as the compound selected as component (2)). (includes those that are in a liquid state) as well as those that are in a liquid state as a solution. ^A typical compound has ^the general formula Ti(OR ² _{) 4} ^{- o} represents a halogen, and n represents a number of O<n4). Specific examples include TiCl ₄ , TiBr ₄ , Ti(O
-nC ₄ H ₉ ) Cl ₃ , Ti(O-nC ₄ H ₉ ) ₂ Cl ₂ , Ti(O-
nC ₄ H ₉ ) ₃ Cl, Ti (O-iC ₃ H ₇ ) ₃ Cl, Ti (O-
iC ₃ H ₇ ) ₂ Cl ₂ , Ti(O-iC ₃ H ₇ )Cl ₃ , Ti(O-
Examples include C ₆ H ₅ ) Cl ₃ and Ti(O—C ₆ H ₅ ) ₂ Cl ₂ . Alternatively, a molecular compound obtained by reacting TiX ₄ (where X represents a halogen) with a so-called electron donor may be used. Specific examples include TiCl ₄・CH ₃ COC ₂ H ₅ , TiCl ₄・CH ₃ CO ₂ C ₂ H ₅ ,
TiCl ₄・C ₆ H ₅ NO ₂ , TiCl ₄・CH ₃ COCl, TiCl ₄・
C ₆ H ₅ COCl, TiCl ₄・C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄・
C ₆ H ₅ NH ₂ , TiCl ₄ ClCO ₂ C ₂ H ₅ , etc. Among the above-mentioned molecular compounds (and titanium compounds), those in a solid state can be used by dissolving them in an appropriate solvent. Typical vanadium compounds include
Examples include _VCl4 , _VOCl3 , _VCl3 , and _VBr4 . Among these compounds, titanium tetrahalide is particularly preferred. 5 Component (5) Component (5), which is used as necessary, is an electron-donating compound. Electron donating compound (hereinafter referred to as electron donor)
Any compound known as , silazane, etc. Specifically, for example, there are the following. (a) Water (b) Alcohols having about 1 to 20 carbon atoms, preferably 3 to 4 carbon atoms
Monohydric or polyhydric alcohols (up to the tetrahydric degree), such as ether alcohols, ester alcohols such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, hexanol, octanol, ethylene glycol,
Ethylene glycol monomethyl ether, ethylene glycol monoacetate, glycerin, etc. (c) Ethers Mono- to tetraethers having about 2 to 20 carbon atoms in total, such as diethyl ether, dibutyl ether, dihexyl ether, tetrahydrofuran, dioxane, trioxane, dioctyl ether, ethylene glycol monomethyl ether (mentioned above), and others. (d) Ketones Ketones with a total carbon number of about 8 to 20, for example,
Acetone, methyl ethyl ketone, etc. (e) Aldehydes Aldehydes with about 1 to 10 carbon atoms, for example,
Acetaldehyde, propionaldehyde, benzaldehyde, and others. (f) Carboxylic acids Mono- to tetracarboxylic acids having about 1 to 20 carbon atoms, such as acetic acid, propionic acid, valeric acid, benzoic acid, phthalic acid, and others. Also included are metal salts of the above carboxylic acids. Examples include calcium acetate, magnesium benzoate, calcium stearate, and the like. (g) Esters Esters of the above alcohols and carboxylic acids, such as methyl acetate, methyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, mono- or dibutyl phthalate,
others. (H) Nitriles Mono- or di-nitriles having about 1 to 20 carbon atoms,
For example, acetonitrile, acrylonitrile,
Benzonitrile, etc. (li) Silanols Silanols having about 1 to 20 carbon atoms in total, such as trimethylsilanol, dimethylsilanediol, phenylsilanetriol, and others. (x) Amines Aniline, triethylamine, acetamide, and others. Among these compounds, water, alcohols, and esters are particularly preferred. 6. Contact (1) Amount Ratio of Components (1) to (4) ((5)) The amount of each component used can be arbitrary as long as the effect of the present invention is recognized, but generally the following It is preferably within the range of . (a) The amount of the titanium alkoxide compound used as component (2) may be within a molar ratio of 1×10 ⁻³ to 50, more preferably 0.1 to ¹⁰ , relative to the magnesium compound component (1). is within the range of (b) Component (3)

The usage amount of the polymeric silicon compound having the structure shown by [Formula] is Si/
The atomic ratio of Mg may be within the range of 1 × 10 ^-3 to 50,
More preferably, it is within the range of 0.1 to 5. (c) The amount of liquid titanium or vanadium halogen compound used in component (4) is based on the magnesium compound component.
The molar ratio to (1) may be within the range of 1×10 ⁻² to 100, more preferably within the range of 0.1 to 10. (d) When using the electron donor of component (5), the amount used may be within the range of 1 x 10 ^-3 to 50 molar ratio to the magnesium compound component (1), and is more preferably is within the range of 0.1 to 10. (2) Contact order The contact order of components (1) to (4) ((5)) may be arbitrary as long as the effect of the present invention is recognized, but typical examples include the following. (a) Components (1) and (2) are brought into contact, and then components (3) and (4) are brought into contact. (b) The method of (b), in which component (1) is treated in advance in (5). (c) After components (1) and (2) are brought into contact, component (5) is brought into contact, and then components (3) and (4) are brought into contact. (d) Components (1), (2), and (5) are brought into contact at the same time, and then components (3) and (4) are brought into contact. (e) One of the components (3) and (4) is brought into contact with each other first using the methods (a) to (d) above. In this way, component (1) is preferably brought into contact with component (2) or with components (2) and (5) before being brought into contact with components (3) and (4). (3) Contact method Components (1) to (4) ((5)) can be brought into contact by any generally known method. Generally -50℃～
Both components may be brought into contact within a temperature range of 200°C.
The contact time is usually about 10 minutes to 5 hours. Components (1) to (4) ((5)) are preferably brought into contact with each other under stirring, and mechanical pulverization using a ball mill, vibration mill, etc. is used to further ensure complete contact between the two components. You can also do that. Further, sufficient contact can also be achieved by dissolving solid component (1) in component (2) and then precipitating it as a solid. Components (1) to (4) ((5)) can also be brought into contact in the presence of a dispersion medium. Dispersion media in this case include hydrocarbons, halogenated hydrocarbons, dimethylpolysiloxane, and the like. Specific examples of hydrocarbons include:
Examples of halogenated hydrocarbons include hexane, heptane, benzene, toluene, and cyclohexane. Specific examples of halogenated hydrocarbons include n-butyl chloride, chloroform, carbon tetrachloride, O-chlorotoluene, m-chlorotoluene, p-chlorotoluene, and chloride. Examples include benzyl, benzylidene chloride, iodobenzene, etc. 7 Polymerization of α-olefin (1) Formation of catalyst The catalyst component of the present invention can be used together with an organometallic compound which is the other catalyst component or cocatalyst to produce α-olefin.
It can be used in the polymerization of olefins. As the organometallic compound used as a cocatalyst, any of the organometallic compounds of groups 1 to 10 of the periodic table, which are known as cocatalysts for Ziegler type catalysts, can be used. Particularly preferred are organic aluminum compounds. Specific examples include the general formula R ³ _3-p AlX _p or
R ⁴ _3-q Al(OR ⁵ ) _q (here, R ³ , R ⁴ , and R ⁵ are hydrocarbon residues having 1 to 20 carbon atoms, which may be the same or different, and X ² is the same as the above X ¹ or different halogen or hydrogen atoms, p and q each 0p
2,0q1). Specifically, (a) trimethylaluminum,
Trialkylaluminum such as triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, (b)
Dialkyl hydride such as diethyl aluminum hydride, diisobutyl aluminum hydride, (iii) diethyl aluminum monochloride, diisobutyl aluminum monochloride,
Examples include alkyl aluminum hydrides such as ethyl aluminum sesquichloride and ethyl aluminum dichloride, and alkyl aluminum alkoxides such as (d)diethyl aluminum ethoxide, diethylaluminum butoxide, and diethylaluminium phenoxide. In addition to these organoaluminum compounds (a) to (d), other organometallic compounds such as R ⁵ _3-n Al(OR ⁶ ) _n (1<m
An alkyl aluminum alkoxide represented by 3) can also be used in combination. For example, combinations of triethylaluminum and diethylaluminium ethoxide, combinations of diethylaluminum monochloride and diethylaluminium ethoxide, combinations of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum monochloride and diethylaluminum ethoxide, etc. Used in conjunction with
can be given. The amount of these organometallic compounds to be used is not particularly limited, but the weight ratio to the solid catalyst component of the present invention is
It is preferably within the range of 0.5 to 1000. (2) α-olefin The α-olefin polymerized using the catalyst system of the present invention is
It is represented by the general formula R--CH=CH ₂ (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and may have a substituent). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methyl-pentene-1. Particular preference is given to ethylene or propylene, especially ethylene. Mixtures of these α-olefins can be used, for example in the case of the polymerization of ethylene, copolymerization with up to 20 weight percent of the above α-olefins, based on ethylene, can be carried out. Furthermore, copolymerization with copolymerizable monomers other than the above-mentioned α-olefins (eg, vinyl acetate, diolefins) can also be carried out. (3) Polymerization The catalyst system of the present invention can of course be applied to ordinary slurry polymerization methods, but it can also be applied to continuous polymerization methods such as liquid-phase solvent-free polymerization methods that do not substantially use solvents or gas-phase polymerization methods. It is applicable to both polymerization, batch polymerization, and prepolymerization. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, and toluene are used alone or in mixtures. Polymerization temperature is from room temperature to about 200℃, preferably from 50℃ to 150℃
℃, and hydrogen can be used as an auxiliary molecular weight regulator at that time. Same or different from component (4) in small amounts for polymerization, etc.
Ti(OR′ ⁾ ₄ ^- _n
By adding a halogen (X' is a halogen which is the same as or different from X, and m is a number of 0 m4), it is possible to control the density of the produced polymer. Specifically, a polymer having a desired density within the range of about 0.890 to 0.965 can be obtained. 8 Experimental Examples Example 1 (1) Production of solid catalyst component 150 ml of thoroughly degassed and purified n-heptane was placed in a 1-liter flask substituted with _N2 , and then anhydrous MgCl ₂ (pulverized for 24 hours in a ball mill) was added. ) and 0.1 mol of Ti(O-nC ₄ H ₉ ) ₄
0.03 mol, respectively, and lowered the temperature to 70℃.
Stirred for 1 hour. Reduce temperature to 50℃, then
0.02 mol of _TiCl4 and methylhydrogen polysiloxane (21 centistokes)
(hereinafter abbreviated as MHPS) was introduced in an amount of 0.12 mol, and stirred for 2 hours. After the stirring was completed, the solid component was used as a catalyst component without being washed with n-heptane. A portion of it was taken and the Ti content in the solid catalyst component was measured by a colorimetric method, and it was found to be 7.1% by weight. (2) Polymerization of ethylene After repeating vacuum ethylene replacement several times into a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, 800 ml of n-heptane that had been sufficiently dehydrated and deoxidized was introduced, and then Triethyl aluminum 100
3.0 mg of the solid catalyst component synthesized above was introduced. The temperature was raised to 85℃, and the partial pressure of hydrogen was 4.5Kg/cm ² .
Further, 4.5 Kg/cm ² of ethylene was introduced to bring the total pressure to 9 Kg/cm ² G. Polymerization was carried out for 1.5 hours.
These were kept under the same conditions during the polymerization. however,
The pressure, which decreased as the polymerization proceeded, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were purged, the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer overnight. 75 g of white polymer was obtained. 25000g of polymer (PE) per 1g of solid catalyst component
[Yield based on catalyst (g.PE/
g・Solid catalyst component (the same applies below) = 25000]. When we measured the melt flow rate (MFR) of this polymer at 190℃ and a load of 2.16Kg, we found that
MFR was 3.1. The bulk specific gravity of the polymer is
It was 0.32 (g/cc). Example 2 (1) Production of solid catalyst In the production of the solid catalyst component of Example-1,
The synthesis was carried out in exactly the same manner except that the amounts of TiCl ₄ and MHPS used were 0.04 mol and 0.16 mol, respectively. After synthesis, 500 ml of n-heptane was introduced to remove unreacted _TiCl4 ,
It was used as a solid catalyst component. (2) Polymerization of ethylene Ethylene polymerization was carried out under exactly the same conditions as in Example-1. 93 g of polymer was obtained [yield based on catalyst = 31000]. MFR=2.9, polymer bulk specific gravity=0.33 (g/cc). Examples 3 to 7 In the production of the solid catalyst component of Example 2, the electron donors shown in Table 1 were added to anhydrous MgCl ₂ and Ti(O-
Production was carried out in exactly the same manner except that nC ₄ H ₉ ) ₄ was stirred at 70° C. for 1 hour and then stirred for an additional 1 hour at the same temperature, and ethylene was polymerized under exactly the same conditions. The results are shown in Table-1.

[Table] Comparative Example 1 In the production of the solid catalyst component of Example-1,
Production was carried out in exactly the same manner except that MHPS was not used, and ethylene polymerization was carried out in exactly the same manner except that the amount of solid catalyst component introduced was 30 mg. 43g of polymer was obtained. Yield to catalyst is 1430
And it was very low. Comparative Example 2 In the production of the solid catalyst component of Example-1,
Production was carried out in exactly the same manner except that Ti(O-nC ₄ H ₉ ) ₄ was not used, and ethylene polymerization was carried out in exactly the same manner except that the amount of solid catalyst component introduced was 50 mg.
Only 6 g of polymer was obtained. Comparative Example 3 In the production of the solid catalyst component of Example-3,
The production was carried out in exactly the same way, except that dimethylpolysiloxane (100 centistocousus) was used instead of MHPS, and the same procedure was carried out, except that the feed amount of the solid catalyst component was 20 mg for the polymerization of ethylene. Ta. 58g of polymer was obtained, MFR=
0.51, and the polymer bulk density was 0.22 g/cc. Example 8 In the production of the solid catalyst component of Example-3,
The amount of TiCl ₄ used was 0.08 mol, and after the synthesis was completed, n-
The preparation was carried out in exactly the same manner, except that it was washed twice with 500 ml of heptane, and the polymerization of ethylene was carried out in the same manner. 211 g of polymer was obtained [yield based on catalyst = 70,000]. MFR=4.8, polymer bulk specific gravity=0.35 (g/cc). Example 9 (1) Production of solid catalyst component Using the equipment used in the production of the solid catalyst component in Example-1, 0.1 mol of MgCl ₂ and Ti(O-
0.15 mol of nC ₄ H ₉ ) ₄ , 0.07 mol of n-BuOH,
Each was introduced and reacted at 80°C for 1 hour. Next, 0.2 mol of MHPS was introduced and reacted at 60°C for 2 hours. Then, the temperature was lowered to room temperature and washed twice with 500 ml of n-heptane. Then 0.02 mol of TiCl ₄ , 0.08 mol of MHPS and
0.01 mol of TBT was introduced into each, and the mixture was reacted at 70°C for 2 hours. A solid catalyst component was obtained without washing with n-heptane. (2) Polymerization of ethylene Ethylene polymerization was carried out under exactly the same conditions as in Example-1. 123 g of polymer was obtained [yield based on catalyst = 41000]. MFR=3.2, polymer bulk specific gravity=0.36 (g/cc). Example 10 In the production of the solid catalyst component of Example-1,
The production was carried out in exactly the same manner, except that Mg(OC ₂ H ₅ ) ₂ was used instead of MgCl ₂ , and the polymerization of ethylene was carried out in the same manner. 73 g of polymer was obtained [yield based on catalyst = 24300]. MFR = 3.0, polymer bulk specific gravity = 0.30 (g/cc) Example 11 In the production of the solid catalyst component of Example-1,
The production was carried out in exactly the same manner except that a pulverized mixture of MgCl ₂ and Mg(OH) ₂ (1:1 by weight, pulverized for 24 hours in a ball mill) was used instead of MgCl ₂ .
Polymerization of ethylene was carried out in exactly the same manner. 68 g of polymer was obtained [yield based on catalyst = 29000]. MFR=3.3, polymer bulk specific gravity=0.31 (g/cc). Examples 12-13 Using the solid catalyst component produced in Example-1,
Ethylene polymerization was carried out under exactly the same conditions using the compounds shown in Table 2 instead of triethylaluminum as the organoaluminum component. The results are shown in Table-2.

[Table] Example 14 Using the solid catalyst component produced in Example-3,
Polymerization was carried out in exactly the same manner, except that an ethylene-butene-1 mixed gas containing 10 volume percent butene-1 was used instead of ethylene, and the polymerization temperature was 65°C. 121 g of polymer was obtained. [Yield vs. catalyst = 40300]. MFR=4.2, polymer bulk specific gravity=0.33 (g/cc). Example 15 (1) Production of solid catalyst component In the production of the solid catalyst component of Example-9,
Production was carried out in exactly the same manner except that 0.1 mol of ethyl benzoate was used instead of n-BuOH.
The Ti content in the solid catalyst component was 3.1 weight percent. (2) Polymerization of propylene Using the autoclave used in Example 1, thoroughly dehydrated and deoxygenated n-heptane was
Then, 114 mg of triethylaluminum, 30 mg of ethyl benzoate, and 50 mg of the above solid catalyst component were each introduced. Polymerization temperature was set to 60℃, propylene 8Kg/cm ² G
Polymerization was carried out for 1 hour. 55 g of polymer was obtained. The weight percent was Total II/Product II = 93/96. Example 16 In the production of the solid catalyst component of Example-1,
The solid catalyst component was produced in exactly the same manner except that VCl ₄ was used instead of TiCl ₄ , and the polymerization of ethylene was carried out in exactly the same manner. 58 g of white polymer was obtained. MFR=1.6, polymer bulk specific gravity=0.31. Example 17 Using the solid catalyst component produced in Example-1,
Ethylene polymerization was carried out in the same manner as in Example 1, except that 20 mg of Ti(O-nC ₄ H ₉ ) ₄ was added to the polymerization system and the polymerization temperature was lowered to 70°C. 72g of white polymer was obtained. The polymer density of this white polymer was measured and found to be 0.923 (g/cc). The polymer density of the white polymer obtained in Example-1 was 0.966.
(g/cc), and it can be seen that this example is lower. Example 18 (1) Production of solid component 150 ml of thoroughly degassed and purified n-heptane was placed in a 1 liter flask purged with nitrogen, and then anhydrous MgCl ₂ (24 mL was added using a ball mill).
0.1 mol of Ti (O-
0.03 mol of nC ₄ H ₉ ) ₄ was introduced, the temperature was raised to 70° C., and the mixture was stirred for 1 hour. Then TiCl ₄
0.02 mol was introduced and stirred for 1 hour. Then n
-0.08 mol of BuOH was introduced and stirred for 1 hour.
Next, 0.15 mol of methylhydrodiene polysiloxane (21 centistokes) was introduced, and the mixture was stirred at 70°C for 2 hours. After the reaction was completed, the solid component was used as a catalyst component without being washed with n-heptane. A portion of it was taken and the Ti content in the solid catalyst component was measured by a colorimetric method, and it was found to be 8.2% by weight. (2) Polymerization of ethylene Into a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, after repeating vacuum-ethylene displacement several times, 800 ml of n-heptane, which had been sufficiently dehydrated and deoxidized, was introduced. , followed by triethylaluminum
100 mg of the catalyst component synthesized above at 3.0
Introduced milligrams. The temperature was raised to 85° C., and hydrogen was introduced at a partial pressure of 4.5 Kg/cm ² and ethylene was introduced at a partial pressure of 4.5 Kg/cm ² to bring the total pressure to 9 Kg/cm ² . Polymerization was carried out for 1.5 hours. These were kept under the same conditions during the polymerization. However, the pressure, which decreases as the polymerization progresses, was kept constant by introducing only ethylene. After the polymerization was completed, ethylene and hydrogen were purged, the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer overnight. 96 grams of white polymer was obtained. 96 grams of white polymer was obtained. This means that 32,000 grams of polymer (PE) were obtained per gram of solid catalyst component. [Catalyst yield (gPE/g solid catalyst component) = 32000]. When the MFR of this polymer was measured at 190°C and a load of 2.16 kg, the MFR was 3.6. The bulk specific gravity of the polymer was 0.33 (g/cc).

[Brief explanation of the drawing]

FIG. 1 is intended to assist in understanding the technical content of the present invention regarding Ziegler catalysts.

Claims (1)

[Scope of Claims] 1. A catalyst component for olefin polymerization, which is a contact product of the following components (1) to (4). Component (1) At least one compound selected from the group consisting of the following magnesium compounds (a) to (f), or a mixture thereof, (a) magnesium dihalide, (b) halohydrocarbyloxymagnesium, (c) magnesium dialcolate, (d) organic acid salt of magnesium, (e) Mg(OH ₂ ), MgO, MgCO ₃ or MgSO ₄ (f) double oxide of magnesium and aluminum or double oxide of magnesium and silicon, (2) a titanium alkoxy group-containing compound; (3) a polymer silicon compound having a structure represented by the following general formula; (Here, R ¹ represents a hydrocarbon residue) (4) Liquid titanium or vanadium halogen compound (However, component (2) and component (4) are not the same).