JPS6338362B2 - - 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. In another aspect, 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 characterized by being a contact product of the following components (1) to (6). 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) a double oxide of magnesium and aluminum or a double oxide of magnesium and silicon, (2) a titanium or silicon alkoxy group-containing compound, (3) a polymeric silicon compound having a structure represented by the following general formula,

[Formula] (R ¹ represents a hydrocarbon residue) (4) Liquid titanium or vanadium halogen compound (Component (2) and (4) are not the same), (5) Inorganic metal halide compounds, (6) 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 six constituent components interact in a complex manner, resulting in a highly active catalyst component. 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. In particular, in many cases, the transition metal component is used in large excess relative to the carrier, so it is necessary to wash the transition metal component, and it is also necessary to treat the unreacted transition metal component. 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. [] Detailed Description of the Invention The catalyst component according to the present invention comprises the following essential components (1) to
It consists of the contact product of (6). 1 Ingredient (1) Ingredient (1) is the following magnesium compound (a) to (f)
At least one compound selected from the group consisting of: or a mixture thereof. (a) Magnesium dihalide For example, MgF ₂ , MgCl ₂ , MgBr ₂ ,
Mgl ₂ , etc. (b) Halohydrocarbyloxymagnesium For example, Mg(OC ₂ H ₅ )Cl, Mg(OC ₆ H ₅ )
Cl, Mg(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 ) ₂ , and others. (E) Mg(OH ₂ ), MgO, MgCO ₃ , and
MgSO ₄ (f) Magnesium and aluminum double oxide,
Double oxide of magnesium and silicon. As a mixture of components (a) to (f), for example,
Mixture of _MgCl2 and Mg _{( OC2H5} ), _MgCl2 and
There are mixtures with Mg(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 or silicon alkoxy group-containing compounds are not only simple alkoxides in which the valences of these metals are filled only with alkoxide groups, but also compounds in which part of the valences are filled with other groups, such as halogen groups. Specific examples include compounds containing alkoxide groups that are filled with Si.
( _{OC2H5 ) 4} , Si(O- _nC4H9 ) ₄ , Ti(OC2H5) ₄ , Ti( _{O -iC3H7 ) 4 , Ti} (O _{- nC4H9} ) ₄ , Ti( _{OC6H5 ) 4} , Si(OC2H5 _{) 3Cl} , Si( _{OC2H5 ) 2Cl2} , Ti ₍ O- _{nC4H9 ) 3Br} , Ti( _{O -} nC4H9 _{) ) 2Cl2Ti} (O- _{nC2H5 ) 2Br2 , Ti} ( _OC2H5 ) _Cl2 , etc. Among these metal alkoxy group-containing compounds, titanium alkoxy group-containing compounds, particularly tetraalkoxy titanium, are preferred. 3 Component (3) General formula

[Formula] (R ¹ represents a hydrocarbon residue) Specific examples of polymer silicon compounds having a structural unit represented by the formula 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 have a large effect on the catalyst component of the present invention,
Preferably it is capped with an inert group such as a trialkylsilyl group. Among these polymeric silicon compounds, alkylhydropolysiloxanes, especially methylhydropolysiloxanes, are preferred. 4 Component (4) A liquid titanium halide 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. Typical compounds have ^the general formula Ti ⁽ OR ² ) _{4 -} ^o , X ¹ represents a halogen, and n represents a number of 0<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−
_iC3H7 ) _Cl3 , Ti ₍ O- _C6H5 ) _Cl3 , _Ti (O-
Examples include C ₆ H ₅ ) ₂ Cl ₂ . Alternatively, a molecular compound obtained by reacting TiX ¹ ₄ (where X ¹ 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) Any compound that is generally known as an inorganic halogen compound can be used (however,
components (1) and (4)). Representative compounds include the following. LiCl, NaCl, KCl, NaBr, KBr, BeCl,
_MgCl2 , _CaCl2 , _SrCl2 , _BaCl2 , _ZrCl4 ,
_MoCl3 , _MoCl5 , _CrCl3 , _MnCl2 , _FeCl2 ,
_FeCl3 , _FeBr2 , _FeBr3 , _CoCl2 , _CoBr2 ,
NiCl ₂ , NiBr ₂ , NiI ₂ , CuCl ₂ , CuCl, CuBr ₂ ,
ZnCl ₂ , ZnI ₂ , AlCl ₃ , AlBr ₃ , AlI ₃ , BCl ₃ ,
_BBr3 , _GeCl2 , _GeCl4 , _SiCl4 , _{Si2Cl6 ,
HSiCl3} , _SnCl2 , _SnCl4 , _PbCl2 , _PbCl4 ,
_InCl3 , _TiCl3 . Among these inorganic halogen compounds, halides of aluminum, iron and titanium are preferred, particularly AlCl ₃ . 6 Component (6) Any compound known as an electron donating compound (hereinafter referred to as an electron donor) can be used, but generally water, alcohols, ethers, ketones, These include aldehydes, carboxylic acids, esters, nitriles, silanols, amines, and silazane. Specifically, for example, there are the following. (a) Water (b) Alcohols 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 having a total carbon number of about 8 to 20, such as acetone, methyl ethyl ketone, and others. (E) Aldehydes Aldehydes with about 1 to 10 carbon atoms, such as acetaldehyde, propionaldehyde,
Benzaldehyde, etc. (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, and others. (H) Nitriles Mono- to dinitrile having about 1 to 20 carbon atoms, such as acetonitrile, acrylonitrile, benzonitrile, and others. (li) Silanols Silanols having about 1 to 20 carbon atoms in total, such as trimethylsilanol, dimethylsilanediol, phenylsilanetriol, and others. (n) Amines Aniline, triethylamine, acetamide, and others. Among these compounds, water, alcohols, and esters are particularly preferred. 7 Contact of components (1) to (6) (1) Amount ratio The amount of each component used can be arbitrary as long as the effect of the present invention is recognized, but it is generally preferable to use within the following range. . (a) The amount of the titanium or silicon alkoxide compound used as component (2) is 1 x 10 ^-3 to 50 molar ratio to the magnesium compound component (1).
It may be within the range of , more preferably 0.1 to
Within the range of 10. (b) Component (3)

The amount of the polymeric silicon compound having the structure represented by the formula may be in the range of 1×10 ^-3 to 50, more preferably in the range of 0.1 to 5, based on the atomic ratio of Si/Mg to the magnesium compound. It is within. (c) The amount of liquid titanium or vanadium halogen compound used as component (4) is 1×10 ^-3 to 1 in molar ratio to magnesium compound component (1).
may be within the range of, more preferably 5×
It is within the range of 10 ^-2 to 4×10 ^-1 . (d) The amount of the inorganic metal halogen compound used as component (5) may be within the range of 1 x 10 ^-4 to 50, more preferably 5 x 10 ^-2 to 50 in molar ratio to the magnesium compound (1). Within the range of 10. (e) The amount of the electron donor used as component (5) is 1× in molar ratio to the magnesium compound component (1).
It may be within the range of 10 ^-4 to 50, more preferably within the range of 5 x 10 ^-2 to 10. (2) Contacting order The contacting order of components (1) to (6) may be arbitrary as long as the effects of the present invention are recognized, but typical examples include the following. (a) Components (1) and (2) are brought into contact, and then component (6)
, then component (5), then components (3) and (4)
or after contacting with component (3), component (4) is contacted. (b) After components (1) and (2) are brought into contact, component (6) is brought into contact, and then components (5), (4) and (3) are brought into contact. (c) Components (1) and (6) are brought into contact, and then component (5),
(4), (3) and (2) are brought into contact. In this way, component (1) is preferably brought into contact with component (2) or with components (2) and (6) before being brought into contact with components (3) and (4). Further, component (5) is preferably brought into contact with component (4) before, after, or simultaneously with component (3). Among the above contact sequences, method (a) is particularly optimal. (3) Contact method Components (1) to (6) can be brought into contact by any generally known method. in general,
Each component may be brought into contact at a temperature range of -50°C to 200°C. The contact time is usually about 10 minutes to 5 hours. Components (1) to (6) are preferably brought into contact with each other under stirring, and further complete contact between the components can be achieved by mechanically pulverizing them using a ball mill, vibration mill, or the like. 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 (6) can also be brought into contact in the presence of a dispersion medium. Dispersion media in this case include hydrocarbons, halogenated hydrocarbons, dihydrocarbyl polysiloxanes, and the like. Specific examples of hydrocarbons include hexane, heptane, benzene, toluene, cyclohexane, etc. Specific examples of halogenated hydrocarbons include:
n-butyl chloride, 1,2-dichloroethane,
Chloroform, carbon tetrachloride, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, benzyl chloride, benzylidene chloride, iodobenzene, etc. Specific examples of dihydrocarbyl polysiloxane include dialkyl polysiloxane, such as dimethyl polysiloxane. , methylphenylpolysiloxane, etc. 8 Polymerization of α-olefin (1) Formation of catalyst The catalyst component of the present invention can be used in the polymerization of α-olefin in combination with an organometallic compound that is the other catalyst component or cocatalyst. 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 ² _p or R ⁴ _3-q Al(OR ⁵ ) _q (where R ³ , R ⁴ , and
R ⁵ has 1 carbon number, which may be the same or different
~20 hydrocarbon residues or hydrogen, X ² as above
There is a halogen which is the same as or different from X ¹ , p and q are the numbers of 0p2 and 0q1, respectively). Specifically, (a) trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum hydride,
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride, (c) alkyl aluminum halides such as diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (d) diethyl aluminum ethoxide, diethyl aluminum butoxide, diethyl Examples include alkyl aluminum alkoxides such as aluminum phenoxide. In addition to these organoaluminum compounds (a) to (d), other organometallic compounds such as R ⁵ _3-n Al(OR ⁶ ) _n
An alkyl aluminum alkoxide represented by (1<m3) 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. Can be used in combination with de. The amount of these organometallic compounds to be used is not particularly limited, but it is preferably within the range of 0.5 to 1000 in weight ratio to the solid catalyst component of the present invention. (2) α-Olefin The α-olefin polymerized using the catalyst system of the present invention has the general formula R-CH=CH ₂ (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and is substituted with may have a group). 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 .alpha.-olefins can be used, for example in the case of ethylene polymerization, copolymerization with up to 20 percent by weight, based on ethylene, of the .alpha.-olefins described above 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 also liquid-phase solventless polymerization methods that do not substantially use solvents,
Whether it is gas phase polymerization, continuous polymerization, batch polymerization, or prepolymerization,
Applicable. As a polymerization solvent in the case of slurry polymerization,
Saturated aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, and toluene may be used alone or in mixtures. Polymerization temperature is from room temperature to about 200℃,
Preferably, the temperature is 50°C to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at that time. Ti (OR′) _4-n X′ _n (here, R′ is the above-mentioned R ¹ to ^{R 6}
The density of the produced polymer is controlled by adding a hydrocarbon residue having about 1 to 10 carbon atoms that is the same as or different from X, X' is a halogen that is the same or different from X, and m is the number of 0 m4. It is possible to do so. 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 Production of catalyst component 150 milliliters of thoroughly degassed and purified n-heptane was placed in a 1-liter flask substituted with nitrogen, and then 0.1 mol of anhydrous MgCl ₂ (pulverized for 24 hours in a ball mill) was added. , Ti(O−nC ₄ H ₉ ) ₄
0.03 mol each was introduced, the temperature was raised to 70 °C,
Stirred for 1 hour. Next, 0.08 mol of n-butanol was introduced and stirred for 1 hour. Then add _0.02 AlCl3
mol was introduced and stirred for 1 hour. Then TiCl ₄
0.02 mol, 21 centistokes of methylhydrodiene polysiloxane (hereinafter abbreviated as MHPS)
0.15 mol each was introduced and 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 the catalyst was taken and the Ti content in the catalyst component was measured by a colorimetric method, and it was found to be 6.3% by weight. Polymerization of ethylene A stainless steel autoclave with an internal volume of 1.5 liters, equipped with stirring and temperature control equipment, was equipped with a vacuum
After repeating ethylene replacement several times, thoroughly dehydrate
800 milliliters of deoxygenated n-heptane was introduced, followed by 100 milligrams of triethylaluminum and 3.0 milligrams of the catalyst component synthesized above. The temperature was raised to 85℃, and the partial pressure of hydrogen was 4.5Kg/cm ² .
Furthermore, 4.5Kg/ ^cm2 of ethylene was introduced, and the total pressure was 9.
Kg/ ^cm2 . Polymerization was carried out for 1.5 hours. These were kept under the same conditions during the polymerization. However, as the polymerization progressed, the pressure decreased, but by introducing only ethylene, the pressure was kept constant. 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.
236 grams of white polymer was obtained. 78,700 grams of polymer (PE) per gram of solid catalyst component
is obtained. [Catalyst yield 1gPE/g
Solid catalyst component) = 78700]. When the melt flow rate (MFR) of this polymer was measured at 190°C and a load of 2.16 kg, the MFR was 4.8. The bulk specific gravity of the polymer was 0.34 (g/cc). Examples 2 to 6 Production of catalyst components In the production of catalyst components in Example 1, the electron donors shown in Table 1 were introduced in place of n-butanol, and the reaction was carried out at 70°C for 1 hour. Catalyst components were produced in the same manner. Polymerization of ethylene Ethylene polymerization was carried out under exactly the same conditions as in Example 1. The results are shown in Table-1. Examples 7 to 12 Catalyst components were produced in exactly the same manner as in Example 1, except that inorganic metal halide compounds shown in Table 2 were used in place of AlCl ₃ . Furthermore, the polymerization of ethylene was carried out in exactly the same manner as in Example 1. The results are shown in Table-2. Examples 13-14 In the production of the catalyst component of Example 1, Ti(O-
_nC4H9 ) ₄ , _n - _C4H9OH , _AlCl3 , _{TiCl4 and}
The catalyst components were produced in exactly the same manner except that MHPS was used in the amount shown in Table 3. Furthermore, the polymerization of ethylene was carried out in exactly the same manner as in Example 1. The results are shown in Table-3. Example 15 A catalyst component was produced in exactly the same manner as in Example 1 except that Mg(OC ₂ H ₅ ) ₂ was used instead of MgCl ₂ . Furthermore, the polymerization of ethylene was carried out in exactly the same manner as in Example 1. 165 grams of polymer was obtained. Ratio to catalyst = 55000, MFR = 3.6, polymer bulk specific gravity =
It was 0.33 (g/cc). Example 16 In the production of the catalyst component in Example 1, except that a pulverized mixture of MgCl _{2 and} Mg(OH) ₂ (weight ratio 1:1, 24-hour ball mill pulverized product) was used instead of MgCl 2. The production was carried out in exactly the same manner, and the polymerization of ethylene was carried out in exactly the same manner. 104 grams of polymer was obtained. Yield vs. catalyst = 48000. MFR=2.6. Polymer bulk specific gravity = 0.33
(g/cc). Examples 17-18 The polymerization of ethylene in Example 1 was carried out in exactly the same manner except that the organoaluminum components shown in Table 4 were used instead of triethylaluminum. The results are shown in Table 4. Example 19 In the ethylene polymerization of Example 7, an ethylene-butene-1 mixed gas containing 10 volume percent of butene-1 was used instead of ethylene, and the polymerization temperature was set at 65%.
The same procedure was carried out except that the temperature was changed to ℃. 136 grams of polymer was obtained. Yield vs. catalyst = 45300. MFR=2.9. . Rimmer bulk specific gravity = 0.36 (g/
cc). Example 20 The catalyst component was produced in exactly the same manner as in Example 1 except that VCl ₄ was used instead of TiCl ₄ , and the polymerization of ethylene was carried out in the same manner. 129 grams of polymer was obtained. Yield vs. catalyst = 43000. MFR=1.8. Polymer bulk specific gravity = 0.31
(g/cc) Example 21 Using the catalyst component produced in Example 1, Ti(O
-nC ₄ H ₉ ) ₄ was added to 20 mg, and the polymerization temperature was increased to 70
Ethylene polymerization was carried out in the same manner as in Example 1 except that the temperature was lowered to .degree. 183 grams of polymer was obtained. Yield vs. catalyst = 61000. The polymer density of this white polymer was measured and found to be 0.928 (g/cc). Note that the polymer density of the white polymer obtained in Example 1 is
0.965 (g/cc), and it can be seen that this example is lower. Example 22 Manufacture of catalyst component The catalyst component of Example 2 was manufactured in exactly the same manner as in Example 2 except that TiCl ₄ .C ₆ H ₅ COOC ₂ H ₅ was used instead of TiCl ₄ . Polymerization of propylene Using the autoclave used in Example 1,
800 ml of sufficiently dehydrated and deoxygenated n-heptane was introduced, followed by triethylaluminum.
114 mg, ethyl benzoate 30 mg,
Fifty milligrams of the solid catalyst components synthesized above were each introduced. The polymerization temperature was set to 60°C, and the polymerization was carried out using 8 kg/cm ² of propylene for 1 hour. 58 grams of polymer was obtained. All II/Product I.
I.=92/96 weight percent. Comparative Example 1 In the production of the catalyst component of Example 1, Ti(O-
A catalyst component was produced in exactly the same manner except that nC ₄ H ₉ ) ₄ was not used, and ethylene polymerization was carried out in the same manner except that the amount of solid catalyst component introduced was 10 mg. 47 grams of polymer was obtained. Catalyst yield =
4700. Comparative Example 2 In the production of the catalyst component of Example 1, MHPS
The catalyst components were produced in exactly the same manner, except that the solid catalyst was not used, and the polymerization of ethylene was carried out in the same manner, except that the amount of solid catalyst introduced was 10 milligrams.
101 grams of polymer were obtained. Catalyst yield =
10100, which was very low. Comparative Example 3 In the production of the catalyst component of Example 1, MHPS
The catalyst components were produced in exactly the same manner, except that dimethylpolysiloxane (100 centistokes) was used instead, and the polymerization of ethylene was carried out in the same manner, except that the amount of solid catalyst introduced was 10 milligrams. 115 grams of polymer was obtained. The yield based on catalyst was 11,500, which was very low. Example 23 In the production of the catalyst component of Example 1, Ti(O-
The polymerization of ethylene was carried out in exactly the same manner except that 0.05 mol of Si(OC ₂ H ₅ ) ₄ was used instead of nC ₄ H ₉ ) ₄ . 97 grams of polymer was obtained. Catalyst yield =
32300. MFR=1.8. Polymer bulk specific gravity = 0.31 (g/
cc). Example ₂₄ In the production of the catalyst component of Example 1, a co-pulverized product of MgCl ₂ and AlCl ₃ (AlCl ₃ content 10
The polymerization of ethylene was carried out in exactly the same manner, except that a 24-hour ball mill (by weight percentage) was used. 176 grams of polymer was obtained. Yield vs. catalyst = 58700. MFR=3.6. Polymer bulk specific gravity = 0.33
(g/cc). Examples 25 to 26 In the production of the catalyst components of Example 1, the amounts of TiCl ₄ used were as shown in Table 5, and the solid components were washed under the conditions shown in Table 5 after catalyst synthesis. The production was carried out in exactly the same manner, and the polymerization of ethylene was carried out in exactly the same manner. The results are shown in Table-5.

【table】

【table】

【table】

【table】

[Table] Example 27 (1) Production of solid component Into a 1 liter flask purged with nitrogen, 150 ml of thoroughly degassed and purified n-heptane was added, and then anhydrous MgCl ₂ (in a ball mill) was added.
0.1 mol of Ti (pulverized for 24 hours) and 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. Then, 0.02 mol of AlCl ₃ 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 6.8% by weight. (2) Polymerization of ethylene Into a stainless steel autoclave with an internal volume of 1.5 liters and equipped with a stirring and temperature control device, after repeating vacuum-ethylene displacement several times, 800 ml of thoroughly dehydrated and deoxidized n-heptane 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. 189 grams of white polymer was obtained. This means that 60,300 grams of polymer (PE) were obtained per gram of solid catalyst component. [Catalyst yield (gPE/g solid catalyst component) = 60300]. When the MFR of this polymer was measured at 190°C and a load of 2.16 kg, the MFR was 4.6. The bulk specific gravity of the polymer was 0.34 (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 (6). 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) Double oxide of magnesium and aluminum or double oxide of magnesium and silicon, (2) ) Titanium or silicon alkoxy group-containing compounds, (3) Polymer silicon compounds having the structure shown by the general formula below, [Formula] (where R ¹ represents a hydrocarbon residue) (4) Liquid titanium or Vanadium halogen compounds (However, component (2) and component (4) are not the same), (5) Inorganic metal halogen compounds, (6) Electron-donating compounds.