JPH0118928B2 - - Google Patents

Description

[Detailed description of the invention]

[] BACKGROUND TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst component that provides a highly active polymer with good polymer properties. Conventionally, magnesium compounds such as magnesium halide, magnesium oxyhalide,
dialkylmagnesium, alkylmagnesium halide, magnesium alkoxide, or
It is known that a highly active catalyst can be obtained by using a complex of dialkylmagnesium and organoaluminum as a carrier for a transition metal compound such as a titanium compound, 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 as follows in slurry polymerization, gas phase polymerization, etc.
extremely important. For example, if the polymer properties are poor, problems such as polymer adhesion within the polymerization tank and failure to extract the polymer from the polymerization tank are likely to occur. 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 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 (A) to (B). Ingredients (A) Magnesium dihalide, titanium tetraalkoxide, and

A solid composition composed of a polymeric silicon compound having the structure: where R is a hydrocarbon residue. Component (B) General formula R ¹ _4-o SiX _o (where R ¹ is hydrogen or a hydrocarbon residue, X is a halogen, n is 1≦n≦
A halogen compound of silicon represented by the number 4). Another catalyst component for olefin polymerization according to the present invention is characterized by being a contact product of the following components (A) to (C). Ingredients (A) Magnesium dihalide, titanium tetraalkoxide, and

A solid composition composed of a polymeric silicon compound having the structure: where R is a hydrocarbon residue. Component (B) General formula R ¹ _4-o SiX _o (where R ¹ is hydrogen or a hydrocarbon residue, X is a halogen, n is 1≦n≦
A halogen compound of silicon represented by the number 4). Component (C) Formula

A polymeric silicon compound having the structure represented by the formula (where R is the same or different hydrocarbon residue as R above). 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 is not necessarily clear, but it is due to the chemical interaction of the components used in the present invention and the special physical properties of the solid component (A) used and the catalyst component produced. This seems to be due to [] Detailed Description of the Invention 1 Component (A) 1 Composition Component (A) is a solid composition composed of magnesium dihalide, titanium tetraalkoxide, and a specific polymeric silicon compound. This solid composition (A) is neither a magnesium dihalide nor a complex of magnesium dihalide and titanium tetraalkoxide, but is another solid. At present, its contents have not been fully analyzed, but according to the compositional analysis results, this solid composition contains titanium, magnesium, halogen, and silicon, and the molar ratio of halogen to magnesium is 0.4 or more and less than 2. It is preferably within the range of 1.0 to 1.8, and seems to be a different compound from the magnesium dihalide used as a raw material. The specific surface area of this component (A) is often small, usually less than 10 m ² /g, and mostly less than 3 m ² /g. Also,
According to the results of X-ray diffraction, no peaks characterizing magnesium dihalide were observed, and even from an X-ray perspective, it seems to be a different compound from magnesium dihalide. 2. Manufacture Component (A) is produced by mutual contact of magnesium dihalide, titanium tetraalkoxide and certain polymeric silicon compounds. (1) Magnesium dihalide Examples include MgF ₂ , MgCl ₂ , MgBr ₂ , etc. (2) Titanium tetraalkoxide For example, Ti(OC ₂ H ₅ ) ₄ , Ti(O-isoC ₃ H ₇ ) ₄ , Ti(O-nC ₄ H ₉ ) ₄ , Ti(O-nC ₃ H ₇ ) ₄ , Ti(O-
isoC ₄ H ₉ ) ₄ , Ti(O-CH ₂ CH(CH ₃ ) ₂ ) ₄ , Ti(OC(CH ₃ ) ₃ ) ₄ , Ti(O-C ₅ H ₁₁ ) ₄ , Ti(O- _C6H13 ) 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 ₈ H ₁₇ ) ₄ , Ti (OC ₁₀ H ₂₁ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] ₄ , etc. (3) Polymer silicon compound formula

In the formula, R is a hydrocarbon residue having about 1 to 10 carbon atoms, particularly about 1 to 6 carbon atoms. Specific examples of polymeric silicon compounds having such structural units include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, and cyclohexylhydropolysiloxane. The degree of polymerization is not particularly limited, but in consideration of handling, it is preferable to have a viscosity of about 10 centistokes to 100 centistokes. Although the terminal structure of the hydropolysiloxane does not have a large effect, it is desirable that it be capped with an inert group such as a trialkylsilyl group. (4) Contact (quantity ratio) of each component The amount of each component used can be arbitrary as long as the effect of the present invention is recognized, but in general,
It is preferably within the following range. The amount of titanium tetraalkoxide used is 0.1 to 10 in molar ratio to magnesium dihalide.
, preferably within the range of 1 to 4. The amount of polymer silicon compound used is 1×10 -2 to 1×10 ⁻² molar ratio to magnesium dihalide.
It may be within the range of 100, preferably within the range of 0.1 to 10. (Contact method) 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. −
The contact may be carried out at a temperature range of 100°C to 200°C, preferably 0°C to 70°C. The contact time is usually about 10 minutes to 20 hours, preferably 0.5 hours to 5 hours. It is preferable to bring the three components into contact with each other while stirring, and they can also be brought into contact by mechanical grinding using a ball mill, vibration mill, or the like. The order of contacting the three components may be arbitrary as long as the effects of the present invention are observed, but it is common to contact the magnesium dihalide and the titanium tetraalkoxide, and then to 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., and specific examples of halogenated hydrocarbons include n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc. Specific examples of dialkylpolysiloxane include dimethylpolysiloxane, methyl-phenylpolysiloxane, and the like. 2. Component (B) Component (B) is a silicon halogen compound. A compound represented by the general formula R ¹ _4-o SiX _o can be used.
(where R ¹ is a hydrogen or hydrocarbon residue,
X is halogen, n is the number 1n4). Specific examples include SiCl ₄ , HSiCl ₃ , CH ₃ SiCl ₃ ,
Examples include SiBr ₄ , (C ₂ H ₅ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, and the like. 3. Component (C) Component (C) is used as necessary.
It is a polymeric silicon compound. This polymeric silicon compound is defined by the same general formula as the polymeric silicon compound to be used for the preparation of component (A). However, the substituent R and the degree of polymerization n may not be the same as those used as component (A). 4 Synthesis of the catalyst component of the present invention The catalyst component of the present invention is composed of components (A) to (B) or components (A) to
It is the contact product of (C). 1 Quantity Ratio The amount of each component to be used is arbitrary as long as the effect of the present invention is recognized, but it is generally preferred to be within the following range. The amount of component (B) used is 1× molar ratio to magnesium dihalide constituting solid component (A).
May be within the range of 10 ^-2 to 100, preferably 0.1 to 10
is within the range of The amount of component (C) used is 1× molar ratio to magnesium dihalide constituting solid component (A).
It may be within the range of 10 ^-3 to 10, preferably within the range of 0.05 to 3.0. 2 Contact method The catalyst component of the present invention is added to the solid component (A) described above.
It is obtained by contacting (B) and optionally component (C). The contacting method can be carried out by any generally known method. The contact may generally be carried out at a temperature range of -100°C to 200°C, preferably 0°C to 70°C. Contact time is usually
The time is about 10 minutes to 20 hours, preferably 0.5 hours to 5 hours. The contact between solid component (A), component (B), and optionally component (C) is preferably carried out under stirring, and can also be brought into contact by mechanical grinding using a ball mill, vibration mill, or the like. The order of contact may be arbitrary as long as the effects of the present invention are observed. Component (B) may be reacted with solid component (A) first, or component (C) may be reacted with solid component (A) first.
Furthermore, components (B) and (C) may be reacted with component (A) simultaneously. Component (A) and components (B) to (C) can also be brought into contact in the presence of a dispersion medium. The dispersion medium in this case can be selected from those exemplified as those to be used when producing component (A). 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. Any of the organometallic compounds of metals from groups 1 to 10 of the periodic table, which are known as cocatalysts, can be used. Particularly preferred are organic aluminum compounds. Specific examples of organoaluminum compounds include the general formula R ³ _3-o AlX _o or R ⁴ _3-n Al(OR ⁵ ) _n (where
R ³ , R ⁴ , R ⁵ have 1 carbon number, which may be the same or different
~20 hydrocarbon residues or hydrogen, X is a halogen atom, n and m are 0n2 and 0, respectively
m1). Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum,
Trialkyl aluminum such as trioctyl aluminum and tridecyl aluminum; (b) alkyl aluminum halides such as diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, and ethyl aluminum dichloride; (c) diethyl aluminum hydride and diisobutyl aluminum Examples include dialkyl hydrides such as hydride, and alkyl aluminum alkoxides such as (d)diethyl aluminum ethoxide, diethyl aluminum butoxide, and diethyl aluminum phenoxide. In addition to these organoaluminum compounds (a) to (c), other organometallic compounds, such as R ⁷ _33-a Al(OR ⁸ ) _a (1a
3, R ⁷ and R ⁸ are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different. 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. 2 α-olefin The α-olefin polymerized with the catalyst system of the present invention is
It is represented by the general formula R-CH=CH ₂ (here, 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-methylpentene-1. Particularly preferred are ethylene and propylene. In the case of these polymerizations, the above α up to 50% by weight, preferably 20% by weight, based on ethylene
-Copolymerization with olefins can be carried out.
Further, 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 be applied not only to ordinary slurry polymerization, but also to continuous polymerization, liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. It is also applicable to batch polymerization or to a method in which prepolymerization is carried out. 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 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. In addition, by adding a small amount of Ti(OR) _4-o X _o (where R 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, it can be controlled within a range of about 0.890 to 0.965. 6 Experimental Examples 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 and Ti(O-nBu) ₄ were introduced. 0.2 mol was introduced and the reaction was carried out at 90°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, and then 12 ml of methylhydrodiene polysiloxane (20 centistokes) was introduced, and the reaction was allowed to proceed for 2 hours. The generated solid component was washed with n-heptane,
When we took out a part and analyzed its composition, we found that Ti
= 14.3% by weight, Cl = 11.7% by weight, Mg = 5.3%, and Si = 1.5% 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. Production of catalyst component 50 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask which had been sufficiently purged with nitrogen, and the entire amount of the solid component (A) synthesized above was introduced thereinto.
0.06 mol of SiCl ₄ and 50 ml of n-heptane were introduced and reacted at 50° C. for 2 hours. After the reaction was completed, it was washed with n-heptane to obtain a catalyst component.
When we took out a part and analyzed its composition, we found that Ti=
3.2 weight percent, Mg=17.5 weight percent,
Cl=49.6 weight percent. 3 Polymerization of ethylene Into a 1.5 liter stainless steel autoclave equipped with stirring and temperature control equipment, after repeating vacuum-ethylene displacement several times, 800 milliliters of thoroughly dehydrated and deoxygenated n-heptane was introduced, followed by Triethyl aluminum 200
milligrams and 10 milligrams of the catalyst component synthesized above were introduced. The temperature was raised to 85° C., hydrogen was introduced at a partial pressure of 4.5 Kg/cm ² , and ethylene was further introduced to bring the total pressure to 9 Kg/cm ² . Polymerization was carried out for 3 hours. These reaction conditions were kept the same during the polymerization. However, the pressure that decreases as the polymerization progresses is
A constant pressure was maintained by introducing only ethylene. After polymerization, purge ethylene and hydrogen and take out the contents from the autoclave.
This polymer slurry was filtered and dried in a vacuum dryer overnight. 116 grams of polymer (PE) was obtained [yield based on catalyst (g PE/g solid catalyst component) = 11600]. When the melt flow rate (MFR) of this polymer was measured at 190°C and a load of 2.16 kg, the MFR was 13.7. The bulk specific gravity of the polymer was 0.48 (g/cc). Example 2 In the production of solid component (A) in Example-1, Ti
(O-nBu) Except that the amount of ₄ used was 0.15 mol,
The solid component (A) was produced in exactly the same manner, the catalyst component was produced in exactly the same manner, and the polymerization of ethylene was carried out in exactly the same manner. 125 grams of polymer was obtained [yield based on catalyst (g・PE/g・solid catalyst component)
=12500〕. MFR=9.7, polymer bulk specific gravity=
It was 0.38 (g/cc). Examples 3-4 In the production of the catalyst component of Example-1, SiCl ₄
The production was carried out in exactly the same manner, except that the amount of introduced and the reaction temperature were changed as shown in Table 1, and the polymerization of ethylene was carried out in the same manner. The results are shown in Table-1. Example 5 In the production of the catalyst component of Example-1, SiCl ₄
The catalyst components were produced in exactly the same manner, except that 0.04 mol of SiCl ₄ and 12 ml of methyl-hydrodiene polysiloxane were each introduced instead, and the reaction was carried out at 70° C. for 2 hours. As a result of composition analysis, Ti=15.5 weight percent, Mg=6.93 weight percent, and Cl=35.8 weight percent.
Polymerization of ethylene was also carried out in exactly the same manner as in Example-1. 53 grams of polymer was obtained [yield based on catalyst (g PE/g solid catalyst component) = 106000]. MFR
= 11.5, polymer bulk specific gravity = 0.45 (g・cc)
It was hot. Examples 6 to 8 The catalyst components of Example 3 were used, except that the organoaluminum components were changed as shown in Table 2.
Polymerization of ethylene was carried out in exactly the same manner. The results are shown in Table-2. Example 9 This example concerns the polymerization of an ethylene-butene-1 gas mixture. Except that the solid component produced in Example-1 was used, an ethylene-butene-1 mixed gas containing 7.5 mol percent of butene-1 was used instead of ethylene, and the H ₂ concentration in the polymerization tank was set to 20 mol percent. carried out polymerization under exactly the same conditions. 256 grams of polymer was obtained. MFR=2.1, polymer bulk density=0.43 (g/cc), polymer density=0.933
(g/cc). Example 10 This example concerns the polymerization of propylene. 800 milliliters of sufficiently dehydrated and deoxygenated n-heptane was introduced into the autoclave used in Example-1, followed by triethylaluminum.
385 mg, 123 mg of ethyl p-toluate, and the catalyst component synthesized in Example-1.
28 milligrams were introduced. Polymerization was carried out at 65° C. and 9 Kg/cm ² for 2 hours. 29 grams of polymer was obtained. T-II = 76% by weight, Product-II
=90% by weight.

【table】

[Table] Examples 11 to 15 In the production of the catalyst component of Example 1,
The synthesis of the solid component (A) and the production of the catalyst component were carried out in the same manner as in Example 1, except that the type and amount of the silicon halogen compound shown in Table 3 was changed in place of _0.06 mol of SiCl 4 . Ethylene polymerization was carried out in the same manner as in Example 1, except that each of the catalyst components listed above was used. The results are shown in Table-3.

【table】 [Brief explanation of drawings]

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 (A) to (B). Component (A) A solid composition composed of a magnesium dihalide, a titanium tetraalkoxide, and a polymeric silicon compound having the structure: where R is a hydrocarbon residue. Component (B) General formula R ¹ _4-o SiX _o (where R ¹ is hydrogen or a hydrocarbon residue, X is a halogen, and n is 1≦n≦4
A halogen compound of silicon, which is the number of . 2. A catalyst component for olefin polymerization, which is a contact product of the following components (A) to (C). Component (A) A solid composition composed of a magnesium dihalide, a titanium tetraalkoxide, and a polymeric silicon compound having the structure: where R is a hydrocarbon residue. Component (B) General formula R ¹ _4-o SiX _o (where R ¹ is hydrogen or a hydrocarbon residue, X is a halogen, and n is 1≦n≦4
A halogen compound of silicon, which is the number of . Component (C) A polymeric silicon compound having a structure represented by the formula (where R is the same or different hydrocarbon residue as R above).