JPH0358369B2 - - Google Patents

Description

[Detailed description of the invention]

[] BACKGROUND TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst component used as a transition metal component of a Ziegler catalyst. Conventionally, when magnesium compounds such as magnesium halides, magnesium oxyhalides, dialkylmagnesium, alkylmagnesium halides, magnesium alkoxides, or complexes of dialkylmagnesium and organoaluminum are used as carriers for transition metal compounds such as titanium compounds, high activity has been achieved. It is known to be a catalyst and many proposals have been made. 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. Poor polymer properties may cause polymer adhesion within the polymerization tank and failure to extract the polymer from the polymerization tank. Further, the polymer concentration in the polymerization tank is closely related to the polymer properties, and if the polymer properties are not good, the polymer concentration in the polymerization tank cannot be increased. The inability to increase the polymer concentration is extremely disadvantageous in industrial production. Prior Art According to Japanese Patent Publication No. 51-37195, a method has been proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide and further reacted with organoaluminium. According to JP-A-54-16393, a method is proposed in which magnesium halide or the like is reacted with titanium tetraalkoxide or the like, and then a halogen-containing compound and a reducing compound are reacted. [] 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 metal catalyst component made 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 (A) to (C). Component (A) The following components (A-1), (A-2) and (A-
3) A solid composition composed of. Component (A-1) Magnesium dihalide. Component (A-2) Titanium tetraalkoxide and (or) general formula

A polytitanate ester represented by the formula (where R ¹ , R ² , R ³ and R ⁴ are hydrocarbon residues, and n represents a number of 2 or more). Component (A-3)

A polymeric silicon compound having the structure represented by the formula (where R ⁵ is a hydrocarbon residue). Component (B) Organoaluminium compound. Component (C) Liquid titanium compound and/or silicon halogen compound. Effects When α-olefin is polymerized using the solid catalyst component according to the present invention as the transition metal component of a Ziegler catalyst, a polymer with high activity and excellent polymer properties can be obtained. The reason why a polymer with high activity and good polymer properties can be obtained by using such a catalyst component is not necessarily clear, but it is important to understand the chemical interaction of the components used in the present invention, the solid component (A) used, and the generated catalyst. This may be due to the special physical properties of the ingredients. It is interesting to use an organoaluminum compound (component (B)) as one of the components constituting the catalyst component of the invention. This is because the organoaluminum compound has been used as a cocatalyst to form a Ziegler catalyst in combination with a transition metal component (the catalyst component of the present invention is also used as a Ziegler catalyst in combination with a cocatalyst). [] Detailed Description of the Invention 1 Component (A) (1) Contents Component (A) consists of component (A-1) and component (A-2).
and component (A-3) are brought into contact with each other. This solid composition (A) is neither magnesium dihalide nor a complex of magnesium dihalide and titanium tetraalkoxide or polytitanate, but is another solid. At present, its contents have not been fully analyzed, but according to the results of compositional analysis, this solid composition contains titanium, magnesium, halogen, and silicon. The specific surface area of this solid component (A) is small in most cases, usually less than 10 m ² /g, and according to the results of X-ray diffraction, there is no peak characteristic of magnesium dihalide in this solid component (A). Therefore, it appears to be a different compound from magnesium dihalide when viewed from X-rays. (2) Component (1) Component (A-1) This is magnesium dihalide, specifically, for example, MgF ₂ ,
There are MgCl ₂ , MgBr ₂ , etc. (2) Component (A-2) This is titanium tetraalkoxide and/or polytitanate ester. _Examples of titanium tetraalkoxide include Ti( _{OC2H5 ) 4} , Ti(O- _iC3H7 ) ₄ ,
Ti(O-nC ₄ H ₉ ) ₄ , Ti(O-nC ₃ H ₇ ) ₄ , Ti
(O- _iC4H9 ) _{4 ,} Ti(O- _CH2CH ( _CH3 ) ₂ ) ₄ ,
Ti(OC _{( CH3} ) ₃ ) ₄ , Ti( _OC5H11 ) ₄ ,
Ti(O-C ₆ H ₁₃ ) ₄ , Ti(O-nC ₇ H ₁₅ ) ₄ , Ti
[OCH(O ₃ H ₇ ) ₂ ] ₄ , Ti[OCH(CH ₃ )
C ₄ H ₉ ] ₄ , Ti (O-nC ₈ H ₇ ) ₄ , Ti
(OC ₁₀ H ₂₁ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ )
C ₄ H ₉ 〕 ₄ , etc. As polytitanate ester,

The formula represented by [Formula] is used. Here, R ¹ to ^{R 4} are hydrocarbon residues, particularly those having about 1 to 20 carbon atoms, especially about 1 to 6 carbon atoms, and n is a number of 2 or more, especially about 2 to 10 carbon atoms. be. Specifically, for example, tetra-normal butyl polytitanate (degree of polymerization n = 2 to 10), tetra-normal hexyl polytitanate (degree of polymerization n = 2 to 10), or tetra-octyl polytitanate (degree of polymerization n = 2). ~10) etc. (3) Component (A-3) This polymer silicon compound has the formula

It has a structure represented by the following formula. Here, R ⁵ has about 1 to 10 carbon atoms,
In particular, about 1 to 6 hydrocarbon residues. Specific examples of polymeric silicon compounds having such structural units include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane,
Examples include cyclohexylhydropolysiloxane. The degree of polymerization of this polymeric silicon compound is not particularly limited, but considering handling, the viscosity should be from 10 centistokes to
It is preferable to have a diameter of about 100 centistokes. Furthermore, although the terminal structure of the hydropolysiloxane does not have a large effect, it is preferable that the terminal structure is blocked with an inert group such as a trialkylsilyl group. (3) Production Component (A) is produced by contacting each component (A-1 to A-3). (1) Amount ratio The amount of each component to be used may be arbitrary as long as the effect of the present invention is observed, but it is generally preferred to be within the following range. The amount of titanium tetraalkoxide and polytitanate ester to be used (total amount if used together) may be in a molar ratio of 0.1 to 10, preferably 1 to 4, relative to magnesium dihalide. The amount of polymer silicon compound used is 1 molar ratio to magnesium dihalide.
It may be within the range of ×10 ^-2 to 100, preferably
It is within the range of 0.1 to 10. (2) Contact method The solid component (A) of the present invention is obtained by contacting the three components described above. Contacting the three components can be carried out by any generally known method. Generally -100℃～
Contact may be made within a temperature range of 200°C. Contact time is usually about 10 minutes to 20 hours. The three components are preferably brought into contact with each other under stirring, and may also be brought into contact by mechanical grinding using a ball mill, vibration mill, or the like. The order of contacting the three components can be arbitrary as long as the effects of the present invention are observed, but by bringing magnesium dihalide and titanium tetraalkoxide into contact,
It is common to then contact the polymeric silicon compound. Contacting the three components can also be carried out in the presence of a dispersion medium. Examples of the dispersion medium in this case include hydrocarbons, halogenated hydrocarbons, dialkylpolysiloxanes, and the like. Specific examples of hydrocarbons include hexane, heptane, toluene, cyclohexane, etc. Specific examples of halogenated hydrocarbons include n-butyl chloride,
1,2-dichloroethylene, carbon tetrachloride,
Specific examples of dialkyl polysiloxanes include dimethyl polysiloxane, methyl-phenyl polysiloxane, and the like. Solid component (A) is freed from unnecessary components such as component (A-
Unreacted components of 2) and (A-3) can be removed by washing. As the cleaning solvent to be used, an appropriate one can be selected from among the above-mentioned dispersion media. Therefore, Narusei (A
If the contact in -1) to (A-3) is carried out in a dispersion medium, cleaning operations can be unnecessary or reduced. 2. Component (B) Specific examples of organoaluminum compounds of component (B) include compounds with the general formula R ⁶ _3-1 AlX ₁ or R ⁷ _3-n Al
(OR ⁸ ) _n (where R ⁶ , R ⁷ , R ⁸ are hydrogen or hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different; X is a halogen atom; 1 and m are each 01<3.0m<3.)
There is something expressed as Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, etc.; (b) diethylaluminum monochloride, dibutylaluminum monourolide, ethylaluminum sesquichloride; Alkyl aluminum halides such as ethyl aluminum dichloride, (c) alkyl aluminum hydrides such as diethyl aluminum hydride, diisobutyl aluminum hydride, diisobutyl aluminum hydride, (d) diethylaluminum ethoxide, ethyl aluminum diethoxide, diethylaluminum phenoxide , alkyl aluminum alkoxides such as diethyl aluminum butoxide, and the like. 3 Component (C) (1) Liquid titanium compound Here, "liquid" refers to titanium compounds that are liquid themselves (including those that are complexed and become liquid), as well as those that are liquid as a solution. It includes things that are. Typical compounds include the general formula Ti
(OR ⁹ ) _4-c X _c (where R ⁹ is a hydrocarbon residue, preferably one having about 1 to 10 carbon atoms,
X represents a halogen, and c represents the number of 0c4). Specific examples include TiCl ₄ , TiBr ₄ , Ti(OC ₂ H ₅ )
Cl ₃ , Ti(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti
(O-iC ₃ H ₇ )Cl ₃ , Ti (O-nC ₄ H ₉ )Cl ₃ , Ti
(O−nC ₄ H ₉ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ )Br ₃ , Ti
(OC ₂ H ₅ ) (OC ₄ H ₉ ) ₂ Cl, Ti(O−nC ₄ H ₉ ) ₃ Cl,
Ti(O- _C6H5 ) _Cl3 , _{Ti (} O- _iC4H9 ) _{2Cl2 ,}
Ti(OC ₅ H ₁₁ )Cl ₃ , Ti(OC ₆ H ₁₃ )Cl ₃ , Ti
(OC ₂ H ₅ ) ₄ , Ti(O-nC ₃ H ₇ ) ₄ , Ti(O-
iC ₃ H ₇ ) ₄ , Ti(O-nC ₄ H ₉ ) ₄ , Ti(O-
iC ₄ H ₉ ) ₄ , Ti[O-CH ₂ CH (CH ₃ ) ₃ ] ₄ , Ti(O
−C ₅ H ₁₁ ) ₄ , Ti(O−C ₆ H ₁₃ ) ₄ , Ti(O−
nC ₇ H ₁₅ ) ₄ , Ti [OCH (C ₃ H ₇ ) ₂ ] ₄ , Ti [OCH
(CH ₃ ) C ₄ H ₉ ] ₄ , Ti (OC ₃ H ₁₇ ) ₄ , Ti
(C ₁₀ H ₂₁ ) ₄ , TI [OCH ₂ CH (C ₂ H ₅ )C ₄ H ₉ ] ₄ ,
etc. In addition, the titanium compound of component (C) is TiX′ ₄
(where X′ represents halogen) and an electron donor such as ester, ketone, ether,
A molecular compound obtained by reacting an acid halide, a nitro compound, etc. may also be used. As a specific example,
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・ClCO ₂ C ₂ H ₅ ,
Examples include TiCl ₄ .C ₄ H ₄ O, etc. (2) Silicon halogen compound A compound represented by the general formula R ¹⁰ _4-b Six _o can be used. (Here, R ¹⁰ is hydrogen or a hydrocarbon residue, especially one having about 1 to 10 carbon atoms, X is a halogen, and b is the number of 1b4.) Specific examples include SiCl ₄ , HSiCl ₃ ,
_{CH3SiCl3 , SiBr4} , _{( C2H5} ) _{2SiCl2 ,}
(CH ₃ ) ₃ SiCl, etc. 4 Preparation of Catalyst Component The catalyst component according to the present invention is produced by bringing the above components (A) to (C) into contact with each other. (1) Amount ratio The amount of each component to be used is arbitrary as long as the effect of the present invention is observed, but it is generally preferred to be within the following range. The amount of organoaluminum compound used as component (B) is 1× molar ratio to the magnesium dihalide used when producing component (A).
May be within the range of 10 ^-2 to 100, preferably 0.1
~10. The amount of liquid titanium compound and silicon halogen compound used as component (C) (total amount if used together) is 1× molar ratio to the magnesium dihalide used when producing component (A). It may be within the range of 10 ^-2 to 100, preferably within the range of 0.1 to 10. (2) Contact method Generally known methods may be used as the contact method. The contact temperature may be -100°C to 200°C, preferably 0°C to 100°C. Contact time is usually about 10 minutes to 100 hours. The contact is preferably carried out under stirring, and may also be carried out by mechanical grinding using a ball mill, vibration mill, or the like. Further, the contact according to the present invention can also be carried out in the presence of a dispersion medium. As the dispersion medium at this time, the same one used when producing component (A) can be used. The order of contact may be arbitrary as long as the effects of the present invention are observed. That is, the three components may be brought into contact at the same time, or the two components may be brought into contact with each other, and then the remaining components may be brought into contact with each other. Alternatively, each component can be divided into parts and the divided parts can be brought into contact with each other in stages. (3) Post-treatment According to a preferred embodiment of the present invention, components (A) to (C)
Unreacted component (A-2) and component (A-3) are washed away from the contact product. The cleaning solvent is a solvent for these components and should be inert, examples of which can be found in the dispersion medium to be used in contacting components (A) to (C). can. Therefore, components (A) to (C)
Carrying out the contact in the presence of a dispersion medium has the advantage that a cleaning effect can be expected when the dispersion medium used is removed after the contact. Note that this washing may also remove unreacted substances of the organoaluminum compound used as component (B). 5 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 as a cocatalyst. As the cocatalyst, any organometallic compound of a metal of Groups 1 to 1 of the Periodic Table known in the field of Ziegler catalysts can be used. Particularly preferred are organic aluminum compounds. Specific examples of organoaluminum compounds include the general formula R ¹¹ _3-p AlX _p or R ¹² _3-q Al(OR ¹³ ) _q
(Here, R ¹¹ , R ¹² , and R ¹³ are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different, or hydrogen, X is a halogen atom, and p and q are numbers where 0p<2 and 0q1, respectively. ). Specific examples include:
(a) Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, etc.; (b) Alkyl such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc. Aluminum halide, (c) alkyl aluminum halide such as diethyl aluminum hydride, diisobutyl aluminum hydride,
(d) Alkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminium butoxide, diethylaluminum phenoxide, and the like. These (a)~
(c) Other organometallic compounds are added to the organoaluminum compound of (c), for example, R ¹⁴ _3-q Al(OR ¹⁵ ) _a (1a
13, R ¹⁴ and R ¹⁵ are hydrocarbon residues having approximately 1 to 20 carbon atoms, which may be the same or different.) Alkylaluminum alkoxides represented by the following can also be used together. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, a combination of triethylaluminum, diethylaluminium chloride and diethylaluminium ethoxide. Can be used in combination with 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. Note that the organoaluminum compound as a cocatalyst may be the same as or different from the organoaluminum compound used as component (B). (2) α-Olefin The α-olefin polymerized using the catalyst system of the present invention has the general formula R ¹⁶ −CH=CH ₂ (where R ¹⁶ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms). ). Specifically, ethylene, propylene, butene-1,
There are olefins such as pentene-1 and hexene-1,4-methylpentene-1. Particularly preferred are ethylene and propylene. In these polymerizations, it is possible to carry out copolymerizations with up to 50 weight percent, preferably 20 weight percent, based on ethylene, of the above alpha-olefins, in particular propylene, butene-1. In addition, copolymerizable monomers other than the above α-olefin (such as vinyl acetate,
Copolymerization with diolefin) can also be carried out. (3) Polymerization The catalyst system of the present invention can be applied not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. It can be applied to continuous polymerization, batch polymerization, or prepolymerization. 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. Polymerization temperature is about room temperature to 200℃, preferably 50℃ to 150℃
In this case, hydrogen can be used as an auxiliary molecular weight regulator. In addition, by adding a small amount of Ti(OR ¹⁷ ) _4-r X _r (where R ¹⁷ is a hydrocarbon residue having about 1 to 10 carbon atoms, It is possible to control the density of the polymer that is polymerized. Specifically from 0.890
It can be controlled within a range of about 0.965. 6 Examples Example 1 (1) Synthesis of solid component (A) 50 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and then 0.1 mol of MgCl ₂ (A-1) and Ti (O
-nBu) ₄ (A-2) was introduced in an amount of 0.21 mol, and the mixture was reacted at 90°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, and then methylhydrodiene polysiloxane (20 centistoke) (A-3)
18 milliliters of was introduced and allowed to react for 3 hours. The generated solid component was washed with n-heptane, a portion of it was taken out, and a compositional analysis was performed.Ti = 13.5% by weight, Cl = 12.5% by weight, Mg = 5.4% by weight, Si =
It was 1.6% by weight. Further, when the specific surface area was measured by the BET method, the specific surface area was too small to be measured, but it is estimated to be about 1 m ² /g. (2) Synthesis of catalyst component 25 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and 2 grams of the solid component (A) synthesized above was introduced. Diethyl aluminum ethoxide (component
(B)) (20 weight percent n-heptane solution)
0.0125 mol was introduced over 30 minutes at 0°C, the temperature was raised to 50°C, and the reaction was carried out for 2 hours. After the reaction was completed, the product was washed with n-heptane. 0.1 mol of TiCl ₄ (component (C)) and 50 ml of n-heptane were mixed and introduced into the flask at 0°C over 30 minutes, followed by reaction at 70°C for 2 hours.
After the reaction was completed, it was washed with n-heptane to obtain a catalyst component. When a portion was taken out and analyzed for composition, it was found that Ti = 14.6% by weight, Mg = 7.8% by weight, and Cl = 46.9% by weight. (3) Polymerization of ethylene Internal volume 1.5 with stirring and temperature control equipment
In a little stainless steel autoclave,
After repeating vacuum-ethylene displacement several times, 80 milliliters of sufficiently dehydrated and deoxygenated n-heptane was introduced, followed by 200 milligrams of triisobutylaluminum (cocatalyst) and 10 milligrams of the catalyst component synthesized above. .
Next, H ₂ was introduced at a partial pressure of 4.5 Kg/cm ² and ethylene was further introduced to give a total pressure of 9 Kg/cm ² .
Polymerization was carried out for 1.5 hours. These reaction conditions were kept the same 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. 165 grams of polymer (PE) were obtained.
[Catalyst yield (gPE/g solid catalyst component) (hereinafter referred to as K) = 16500]. When the melt flow rate (MFR) of this polymer was measured at 190°C and a load of 2.16 kg, the MFR was 5.4. The bulk specific gravity of the polymer was 0.370 (g/cc). Example 2 In the production of the catalyst component of Example 1, the amount of diethylaluminium ethoxide (component (B)) introduced was
The production was carried out in exactly the same manner except that the amount was changed to 0.025 mol. Polymerization of ethylene was carried out in exactly the same manner.
220 grams of polymer was obtained. K=22000. MFR=3.4. Polymer bulk specific gravity = 0.374 (g/cc). Examples 3 to 5 The catalyst components of Example 1 were produced in the same manner as in Example 1, except that the type of organoaluminum compound of component (B) was changed as shown in Table 1. Polymerization of ethylene was carried out in exactly the same manner. The results are shown in Table-1. Example 6 In the production of the catalyst component of Example 1, component (C)
The production was carried out in exactly the same manner except that SiCl ₄ was used instead of TiCl ₄ . The Ti content in the catalyst was 3.7 weight percent. Polymerization of ethylene was carried out in exactly the same manner. 161 grams of polymer was obtained. K=16100. MFR=4.2. Polymer bulk specific gravity =
0.388 (g/cc). Example 7 (1) Synthesis of solid component (A) 50 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and then 0.1 mol of MgCl ₂ was introduced.

68 milliliters of [Formula] (R=n-C ₄ H ₉ ) was introduced, and the mixture was reacted at 90° C. for 2 hours. After the reaction was completed, the temperature was lowered to 40° C., and then 18 milliliters of methylhydrodiene polysiloxane (20 centistokes) was introduced and the reaction was allowed to proceed for 2 hours. The produced solid component was washed with n-heptane and a portion thereof was taken out and analyzed for composition, and it was found that Ti was 13.5% by weight. (2) Synthesis of catalyst component 25 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and 20 grams of the solid component (A) synthesized above was introduced. Diethylaluminum ethoxy (component
(B)) (20 weight percent n-heptane solution)
0.0125 mol was introduced over 30 minutes at 0°C, the temperature was raised to 50°C, and the reaction was carried out for 2 hours. After completion of the reaction n-
Washed with heptane. SiCl ₄ (component (C)) 0.0125 mol and n-heptane 10
Milliliter was mixed, introduced into the flask at 30°C, and reacted at 50°C for 1 hour. After the reaction was completed, it was washed with n-heptane. Then _TiCl4
0.1 mol of (component (C)) and 50 ml of n-heptane were mixed and introduced into this flask at 0°C over 30 minutes, followed by reaction at 70°C for 2 hours. After the reaction was completed, the product was washed with n-heptane and used as a catalyst component. When we took out a part of it and analyzed its composition, we found that Ti = 8.7% by weight, Mg =
14.7% by weight, Cl=58% by weight. (3) Polymerization of ethylene Polymerization was carried out under exactly the same conditions as in Example 1. 197 grams of polymer was obtained. K=19700. MFR=2.3. Polymer bulk specific gravity =
0.379 (g/cc) Example 8 (1) Synthesis of catalyst component In the same manner as in Example 1, solid component (A) and diethylaluminium ethoxide (component (B)) were reacted. Next, 0.0125 mol of SiCl ₄ (component (C)) and 10 ml of n-heptane were mixed, introduced at 30°C, and reacted at 50°C for 1 hour. After the reaction is complete,
The product was washed with n-heptane. Then,
Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] ₄ (Component (C)) 0.0125
mol was introduced at 30°C and reacted at 50°C for 1 hour. Next, 0.1 mol of TiCl ₄ (component (C)) and 50 ml of n-heptane were mixed, introduced at 0°C over 30 minutes, and reacted at 70°C for 2 hours. After the reaction was completed, the product was washed with n-heptane and used as a catalyst component. When we took out a part of it and analyzed its composition, we found that Ti = 9.7% by weight, Mg
= 12.4 weight percent, Cl = 38.5 weight percent. (2) Polymerization of ethylene Polymerization was carried out under exactly the same conditions as in Example 1. 169 grams of polymer was obtained. K=16900. MFR=3.3. Polymer bulk specific gravity =
0.389 (g/cc). Example 9 In the synthesis of the catalyst component of Example 8, Ti
[OCH ₂ CH (O ₂ H ₅ ) C ₄ H ₉ ] ₄ instead of (component (C))
The synthesis was carried out in exactly the same manner except that Ti(Oi-C ₃ H ₇ ) ₄ was used, and the polymerization of ethylene was carried out in the same manner. 191 grams of polymer was obtained. K=19100. MFR=2.9. Polymer bulk specific gravity = 0.32
(g/cc). Examples 10 to 13 Polymerization was carried out in exactly the same manner as in Example 1, except that the organoaluminum compound components were changed as shown in Table 2. Table the results.
Shown in 2. Example 14 This example concerns the polymerization of an ethylene-butene-1 gas mixture. Using the solid component prepared in Example 2, butene-1 was added instead of ethylene.
Ethylene-butene-1 containing 6.0 mole percent
Polymerization was carried out under exactly the same conditions except that a mixed gas was used and the H ₂ concentration in the polymerization tank was set to 25 mol percent. 315 grams of polymer was obtained.
MFR=2.5. Polymer bulk specific gravity = 0.363 (g/cc). Polymer density = 0.935 (g/cc). Example 14 In the production of the catalyst component of Example 6, SiCl ₄ 0.1
A catalyst component was produced in the same manner as in Example 6, except that 0.25 mol of (CH ₃ )SiCl ₃ was used instead of mol. The Ti content in the catalyst was 3.9 weight percent. Polymerization of ethylene was carried out in exactly the same manner as in Example 6, except that this catalyst component was used. 95 grams of polymer was obtained. K=9500, MFR=4.8, polymer bulk specific gravity=0.40 (g/cc).

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart to help understand the technical content of the present invention regarding a Ziegler type catalyst.

Claims (1)

[Scope of Claims] 1. A catalyst component for olefin polymerization, which is a contact product of the following components (A) to (C). Component (A) The following components (A-1), (A-2) and (A-
3) A solid composition consisting of: Component (A-1) Magnesium dihalide. Component (A-2) Titanium tetraalkoxide and/or polytitanate ester represented by the general formula [Formula] (where R ¹ , R ² , R ³ and R ⁴ are hydrocarbon residues, and n is 2 or more). Component (A-3) A polymeric silicon compound having a structure represented by the formula (where R ⁵ is a hydrocarbon residue). Component (B) Organoaluminium compound. Component (C) Liquid titanium compound and/or silicon halogen compound.