JPH0134247B2 - - Google Patents

Description

[Detailed description of the invention]

[Background of the Invention] Technical Field The present invention relates to a catalyst component that provides a highly active polymer with good polymer properties. Conventionally, 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. 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 organoaluminum. 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 (C). Component (A) Magnesium dihalide, titanium tetraalkoxide, and

A solid composition composed of a polymeric silicon compound having a structure represented by the formula: Component (B) Titanium tetrahalide compound component (C) Formula

A polymeric silicon compound having the structure of [Formula] (wherein each R is the same or different hydrocarbon residue) Effects Using the solid catalyst component according to the present invention as the transition metal component of a Ziegler catalyst When olefin is polymerized, 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 four 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 the characteristics. [] 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 5 m ² /
g or less, and most of them are less than 3 m ² /g. Furthermore, 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) Production 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-
_CH2CH ( _CH3 ) ₂ ) ₄ , Ti(OC( _CH3 ) 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 _{( CH3} ) _C4H9 ] ₄ ,Ti _{( OC8H17} ) ₄ ,Ti
(OC ₁₀ H ₂₁ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ )
C ₄ H ₉ ] There are 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,
Examples include cyclohexylhydropolysiloxane. The degree of polymerization is not particularly limited, but considering handling, the viscosity is 10
Preferably, it is about centistokes to 100 centistokes. Further, although the unterminated structure of the hydropolysiloxane does not have a large effect, it is desirable that it is blocked with an inert group such as a trialkylsilyl group. (4) Contact (amount ratio) of each component The amount of each component used can be arbitrary as long as the effect of the present invention is recognized.
Generally, it is preferably within the following range. The amount of titanium tetraalkoxide used is
The molar ratio to magnesium dihalide may be within the range of 0.1 to 10, preferably,
It is within the range of 1 to 4. 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. (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 made 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 the dialkylpolysiloxane include dimethylpolysiloxane, methyl-phenylpolysiloxane, and the like. 2 Synthesis of Catalyst Component of the Present Invention The catalyst component of the present invention is a contact product of the component (A), titanium tetrahalide (component (B)), and a specific polymeric silicon compound (component (C)). (1) Titanium tetrahalide compound (component (B)) Examples include titanium tetrachloride, titanium tetrabromide, and others. Liquid compounds are preferred. (2) Polymer silicon compound formula

In [Formula], R has about 1 to 10 carbon atoms, which is the same as or different from R for component (A), especially 1 to 10 carbon atoms.
There are about 6 hydrocarbon residues. 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. Further, although the unterminated structure of the hydropolysiloxane does not have a large effect, it is desirable that it is blocked with an inert group such as a trialkylsilyl group. (3) Contact between solid component (A) and each component (1) Amount ratio The amount of each component to be used is arbitrary as long as the effect of the present invention is recognized, but generally it is within the following range. is preferred. The amount of titanium tetrahalide (B) to be used may be in a molar ratio of 1 x 10 ^-2 to 10, preferably in a range of 0.1 to 1.0, relative to the magnesium dihalide constituting the solid component (A). It is within. The amount of the polymer silicon compound (C) to be used may be in a molar ratio of 1 x 10 ^-3 to 10, preferably in a range of 0.05 to 1.0, relative to the magnesium dihalide constituting the solid component (A). It is within. (2) Contact method The catalyst component of the present invention is the solid component (A) described above.
It is obtained by bringing two components into contact with each other. The contacting method can be carried out by any generally known method. In general, -
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. The contact between the solid component (A) and the two components is preferably carried out under stirring, and is preferably carried out using a ball mill,
By mechanical grinding using a vibrating mill etc.
It can also be brought into contact. The order of contact is
Any material may be used as long as the effect of the present invention is recognized. The solid component (A) may be reacted with titanium tetrahalide or with a polymer silicon compound first. Further, titanium tetrahalide and the polymer silicon compound may be reacted simultaneously. Components (A) to (C) can also be brought into contact 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,
Examples include methyl-phenyl polysiloxane. The contact product, i.e. the catalyst composition of the invention, is
It has a relatively small surface area, less than 20 m ² /g. 3 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−nAlXn or R ⁴ 3−mAl
(OR ⁵ )m (where R ³ , R ⁴ , R ⁵ are hydrogen or hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different; X is a halogen atom; n and m are each 0n<2 , 0m1). Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride,
Alkyl aluminum halides such as ethyl aluminum dichloride, (c) dialkyl hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, (d) alkyl aluminum alkoxides such as diethyl aluminum ethoxide, diethylaluminum butoxide, and diethylaluminum phenoxide, etc. can give. Other organometallic compounds may be added to these organoaluminum compounds (a) to (c), such as R ⁷ 3−aAl.
An alkyl aluminum alkoxide represented by (OR) ⁸ a (1a3, R ⁷ and R ⁸ are hydrocarbon residues having about 1 to 20 carbon atoms which may be the same or different) can also be used in combination. For example, the combination of triethylaluminum and diethylaluminum ethoxide,
Examples include a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, and a combination of triethylaluminum, diethylaluminum chloride, and diethylaluminium ethoxide. 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, bentene-1, hexene-1, and 4-methylbentene-1. Particularly preferred are ethylene and propylene. In these polymerizations, up to 50% by weight, preferably 20% by weight, of the α-
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 is of course applicable to ordinary slurry polymerization, but can also be continuously applied to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. It can be applied to polymerization, batch polymerization, or prepolymerization. As a polymerization solvent in the case of slurry polymerization,
Saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene may be used alone or in mixtures. The polymerization temperature is from room temperature to about 200°C, preferably from 50°C to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time. Also, during polymerization, a small amount of Ti(OR) ₄ -nXn (where R is a hydrocarbon residue having about 1 to 10 carbon atoms,
is a halogen, n is the number 0n4), it is possible to control the density of the polymerized polymer. in particular
It can be controlled within a range of about 0.890 to 0.965. 4 Experimental 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 and Ti(O _-o Bu) ₄ to 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 produced solid components were washed with n-heptane, and a portion was taken out for compositional analysis, which revealed that Ti = 14.3% by weight, Cl = 11.7% by weight, Mg = 5.3% by weight, and Si = 1.5% by weight. Also,
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 that had been sufficiently replaced with hydrogen storage, and the entire amount of the solid component (A) synthesized above was introduced. Next, 0.04 mol of TiCl ₄ and 50 ml of n-heptane were introduced, followed by 12 ml of methylhydrodiene polysiloxane, and the mixture was reacted at 70° C. for 2 hours. After the reaction is complete, n
- Washed with heptane to obtain a catalyst component. When we took out a part of it and analyzed its composition, we found that Ti
= 14.9 weight percent, Cl = 31.2 weight percent, Mg = 5.9 weight percent and Si = 6.6 weight percent. Also, by the BET method,
When the specific surface area was measured, it was 5.6 (m ² /g). (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, thoroughly dehydrated and deoxygenated n-heptane was
milliliter, followed by 200 milligrams of triethylaluminum and 10 milligrams of the catalyst component synthesized above. 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, 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. 105
grams of polymer (PE) were obtained. The yield to catalyst (gPE/g solid catalyst component) is 10,500. For this polymer, load 2.16Kg at 190℃
When the melt flow ratio (MFR) was measured, it was 7.2. Polymer bulk specific gravity =
It was 0.47 (g/cc). When the particle size distribution of the polymer was measured, it was as follows.

[Table] Examples 2 to 4 The catalyst components were produced in exactly the same manner as in Example 1, except that the amount of TiCl ₄ introduced was changed as shown in Table 1, and the polymerization of ethylene was carried out in the same manner. Ta. The results are shown in Table-1. Examples 5 to 7 The catalyst component was produced in exactly the same manner as in Example 1, except that the amount of methylhydrodiene polysiloxane introduced was changed as shown in Table 2.
Polymerization of ethylene was carried out in exactly the same manner. The results are shown in Table-2. Examples 8 to 11 In the production of the solid component (A) in the production of the catalyst component in Example 1, the same procedure was followed except that the amounts of titanium tetraalkoxide and methylhydrodiene polysiloxane introduced were as shown in Table 3. The solid component (A) was produced, and the catalyst component was produced in exactly the same manner. Furthermore, the polymerization of ethylene was carried out in exactly the same manner. The results are shown in Table-3. Example 12 The catalyst components were produced in exactly the same manner as in Example 1, except that TiCl ₄ and methylhydrodiene polysiloxane were diluted with 50 ml of n-heptane and the polymerization of ethylene was carried out in the same manner. Ta. 95 grams of white polymer was obtained (yield based on catalyst=9500 (g PE/g solid catalyst component)).
MFR=9.6 and polymer bulk density=0.47 (g/cc). Example 13 The production of the catalyst component in Example 1 was carried out in exactly the same manner except that Ti(O-iC ₃ H ₇ ) ₄ was used instead of Ti(O-nC ₄ H ₉ ) ₄ , and ethylene polymerization was also carried out. I did exactly the same thing. 92 grams of white polymer was obtained (yield based on catalyst = 9200 (g PE/g solid catalyst component)). MFR=8.5, polymer bulk density=0.45
(g/cc). Example 14 (1) Production of catalyst component 50 ml of dehydrated and deoxygenated n-heptane was introduced into a flask that had been sufficiently purged with nitrogen, and then 12 ml of methylhydrodiene polysiloxane was introduced, and the temperature was raised to 40°C. Next, a reactant of 0.1 mol of MgCl ₂ , 0.2 mol of Ti(O-nC ₄ H ₉ ) ₄ and 50 ml of n-heptane, which had been reacted in advance, was introduced into the flask.
The reaction was carried out at 40°C for 1 hour. After that, Example 1
The catalyst components were produced in exactly the same manner as in the previous example. Note that the Ti content in the catalyst component was 15.2% by weight. (2) Polymerization of ethylene Ethylene polymerization was carried out under exactly the same conditions as in Example 1 except that the organoaluminum component was changed from triethylaluminum to 300 mg of triisobutylaluminum. 91 grams of white polymer was obtained [yield based on catalyst = 9100
(gPE/g solid catalyst component)]. MFR=9.8 and polymer bulk density=0.46 (g/cc). Examples 15 to 17 Ethylene polymerization was carried out in the same manner as in Example 1 except that the catalyst of Example 1 was used and the organoaluminum components were changed as shown in Table 4. Table 4 shows the results.
Shown below. Comparative Example 1 (1) Production of catalyst component In the production of the catalyst component of Example 1, Example 1 was used except that solid component (A) was used as it was without washing with n-heptane after production.
The catalyst components were produced in exactly the same manner as in the previous example. Note that the Ti content in the catalyst component was 12.7% by weight. (2) Polymerization of ethylene Polymerization was carried out under exactly the same conditions as in Example 1. 34 grams of polymer was obtained (yield based on catalyst = 3400 (g PE/g solid catalyst component)). MFR＝
4.3, polymer bulk density = 0.253 (g/cc). The polymer particle size distribution was as follows.

[Table] Example 18 Polymerization of ethylene-butene-1 mixed gas Using the solid component produced in Example 1, using an ethylene-butene-1 mixed gas containing 7.5 mol percent of butene-1 instead of ethylene, Except that the _H2 concentration in the polymerization tank was set to 20 mol percent.
Polymerization was carried out under exactly the same conditions. 178 grams of polymer was obtained. MFR=2.3, polymer bulk density=0.45 (g/cc), polymer density=0.934
(g/cm ³ ).

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【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart to help understand the technical contents 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 (C). Component (A) A solid composition composed of magnesium dihalide, titanium tetraalkoxide, and a polymeric silicon compound having the structure represented by the formula. Component (B) Titanium tetrahalide compound Component (C) Polymer silicon compound having a structure represented by the formula (wherein each R is the same or different hydrocarbon residue)