JPH0317842B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing olefins, particularly ethylene or ethylene and other 1-olefins. Specifically, it is a novel method characterized by using a solid catalyst component that is a mixture of a specific titanium- or panadium-containing magnesium compound and a chromium-containing solid reacted with a specific organometallic compound.
The present invention relates to an olefin polymerization method for obtaining a polymer having high activity and a wide molecular weight distribution. (Prior art) In the polymerization of olefins, especially ethylene or ethylene and other 1-olefins, Ziegler type catalysts containing titanium, vanadium or a mixture thereof and inorganic oxides are used as a technology to obtain polymers with a wide molecular weight distribution. A technique is known in which a Phillips-type catalyst containing a chromium compound is used at the same time. Specifically, a technique for blending the two is disclosed in JP-A-57-139102, and a technique for ball-milling the two is disclosed in JP-A-59-168001.
No. 59-168002. (Problems to be Solved by the Invention) With the above-mentioned conventional technology, it is true that the molecular weight has been reduced to a molecular weight suitable for molding processing, and has a wide molecular weight distribution and fluidity suitable for blow molding and extrusion molding. ing. However, since catalyst production requires complicated operations such as co-pulverization, and Phillips catalyst is a highly oxidizing substance, it poisons the Ziegler catalyst when mixed, and in areas where there are many Phillips catalysts with a wide molecular weight distribution. There were problems such as insufficient activity. (Means for Solving the Problems) As a result of repeated research to solve the above problems, the inventors of the present invention discovered that the Phillips catalyst side was reacted with a specific organometallic compound before being mixed with the Ziegler catalyst. They discovered that by doing this, a polymer with high activity and a wide molecular weight distribution could be obtained, leading to the present invention. That is, the present invention provides (A) (i) a hydrocarbon-insoluble solid obtained by the reaction of (a) a hydrocarbon-soluble organomagnesium compound or complex compound and (b) a chlorosilane compound containing an Si-H bond; ) A solid component (i) consisting of a halogen atom-containing titanium or vanadium compound, and (ii) (a) a chromium compound supported on (b) an inorganic oxide carrier.
Using a catalyst consisting of a catalyst solid component (A) obtained by mixing the solid obtained by firing with (c) a solid component (ii) reacted with an organometallic compound, and (B) an organometallic compound. The present invention relates to an olefin polymerization method characterized by the following. The present invention will be explained in detail below. The hydrocarbon-soluble organomagnesium compound or complex compound used in the present invention (A)(i)(a) includes:
General formula M〓Mg〓R ¹ _p R ² _q X _r Y _s (where α is 0 or a number greater than 0, β is a number greater than 0, p, q,
r and s are 0 or a number larger than 0, p+q+r+
It has the relationship s=mα+2β, where M is aluminum,
an atom selected from zinc, boron, beryllium and lithium, m represents the valence of M, R ¹ , R ²
are hydrocarbon groups with the same or different number of carbon atoms,
X and Y are the same or different groups, OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a group, R ³ ,
R ⁹ is a hydrocarbon group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms or hydrocarbon groups. Preferably, M is aluminum,
X, Y are OR ³ or OSiR ⁴ R ⁵ R ⁶ , β/α≧1,
It is recommended that (r+s)/(α+β)≦1. The synthesis of these hydrocarbon-soluble organomagnesium compounds or complex compounds is generally known, and may be carried out, for example, according to the publications, gazettes, documents, etc. listed below. That is, M
is aluminum and α>0 is JP-A-50-
Publication No. 139885, Japanese Unexamined Patent Application Publication No. 18235-1987, Publication No. 18235, Publication No.
Publication No. 47-24009, Annarenderhiemi 605
Volume 93-97 (1957), Japanese Patent Application Laid-Open No. 154388-1988,
It may be synthesized from the corresponding organomagnesium and organoaluminium with reference to JP-A-50-157490 and JP-A-53-40696. If M is zinc, boron, beryllium, etc. and α>0, Tokukai 1975
It may be synthesized from corresponding organomagnesium, organozinc, etc. with reference to JP-A-150786, JP-A-51-97687, JP-A-51-107384, and JP-A-52-71421. In addition, those with α=0 that are soluble in hydrocarbons are, for example, n-butyl ethylmagnesium, n-butyl sec-butylmagnesium, n-butyl sec-butylmagnesium,
-butyl iso-propyl magnesium, etc.
JP-A-54-12327, JP-A-56-26893, U.S. Patent No. 4127507, U.S. Patent No.
33646231 specification, US Patent No. 3766280 specification,
Journal of Organic Chemistry No. 34
Volume 1116-1121 (1969), Journal of
It may be synthesized using a corresponding Grignard compound or alkyl lithium compound with reference to Organometallic Chemistry Vol. 64, pp. 25-40 (1974). General formula H _a SiCl _b R _4-(a+b) used in the present invention (A)(i)(b)
The Si-H bond-containing chlorosilane compound represented by R is a hydrocarbon group, a>0, b>0, a+
There is no particular restriction as long as b≦4, but preferably 0
<a<2, and particularly preferred chlorosilane compounds include trichlorosilane and monomethyldichlorosilane. The halogen-containing titanium or panadium compound used in the present invention (A)(i)(c) is not particularly limited as long as it is a titanium or panadium compound containing a halogen atom.
nCla‐n (where n=0≦n≦2, a is 2≦a≦
4 and R represents a hydrocarbon group), and a titanium compound represented by the general formula VO(OR)
mClb-m (where m is 0≦m≦2, b is 1≦b≦
3 and R represents a hydrocarbon group). Preferably, titanium tetrachloride, butoxytitanium trichloride, dibutoxytitanium dichloride, vanadium oxytrichloride, and titanium or vanadium compounds obtained by reducing these with organoaluminum compounds such as triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, etc. These can be used alone or in combination. The chromium compound used in the present invention (A)(ii)(a) is a chromium oxide or a compound that at least partially forms chromium oxide upon calcination, such as a chromium halide, oxyhalide, or nitrate. , acetate, sulfate, oxalate, alcoholate, etc., specifically chromium trioxide, chromyl chloride, potassium dichromate, ammonium chromate, chromium nitrate, chromium acetate, chromium acetylacetonate, ditersia. Examples include butylchromate. Chromium trioxide, chromium acetate, and chromium acetylacetonate are particularly preferably used. As the inorganic oxide carrier used in the present invention (A)(ii)(b), silica, alumina, silica-alumina, zirconia, thoria, etc. can be used, but silica and silica-alumina are preferable, and commercially available Highly active catalytic silica (high surface area, high porosity volume) is particularly preferred. Next, the organometallic compound used in (A)(ii)(c) will be explained. Examples of organometallic compounds include organoaluminum compounds, organoboron compounds, organozinc compounds, organolithium compounds, hydrocarbon-soluble organomagnesium compounds or complex compounds, and preferably organoaluminum compounds,
Examples include hydrocarbon-soluble organomagnesium compounds or complex compounds, and organoboron compounds. Particularly preferably, the general formula AlR ¹⁰ _x (OR ¹¹ ) _y (OSi・H・
An organoaluminum compound containing both an alkoxy group and a hydroxyloxy group represented by R ¹² R ¹³ ) _z is mentioned, and this compound will be explained below. In the above formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent the same or different hydrocarbon groups having 1 to 20 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, and dodecyl, cycloalkyl groups such as cyclohexyl and methylcyclohexyl, and aryl groups such as phenyl, preferably having 2 to 10 carbon atoms. is an alkyl group. Regarding x, y, z, x+y+z=3, x=1, 2≧y
A range of ≧0, 2≧z≧0 is used. Preferably x≧1.5, 1.5≧y≧0.25, 1.5≧z≧0.15 and 1.5
≧y+z≧0.5, particularly preferably x≧2, 1≧y≧0.5, 1≧z≧0.25 and 1 in terms of activity.
A range of ≧y+z≧0.75 is recommended. The above organoaluminum compound containing both an alkoxy group and a hydroxyloxy group may be synthesized, for example, by the following method. Method A. A hydrosiloxy group-containing organoaluminum compound obtained by reacting trialkylaluminum or dialkylaluminium hydride with poly(or oligo)hydrosiloxane in a desired ratio is quantitatively reacted with alcohol (including phenol). OR
Introduce groups. Method B. A hydrosiloxy group is introduced by reacting an OR group-containing organoaluminium compound such as a dialkylaluminum alkoxide with a poly(or oligo)hydrosiloxane in a desired amount ratio. Regarding the first stage of method A, the applicant's patent publication
46-40334 and US Pat. No. 3,661,878, it is described in detail together with the NMR spectrum of the reactant, and is well known. That is, the reaction may be carried out with or without a hydrocarbon solvent at a temperature of room temperature to 200° C. for several hours to several tens of hours under an inert atmosphere. The latter part of Method A is preferably carried out by a conventional method in which an alcohol is added dropwise to an organoaluminum compound to react in the presence of a hydrocarbon solvent.
Although there are no particular restrictions on temperature and time, it is preferably carried out by cooling to room temperature or below. Method B is also carried out in the same manner as the first step of method A. Examples of organoaluminum compounds used as raw materials in Method A or Method B include trimethylaluminum, triethylaluminum, trin-
Examples include propylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, triphenylaluminum, diethylaluminium ethoxide, diethylaluminum n-butoxide, diisobutylaluminum ethoxide, and mixtures thereof. It will be done. Alcohols (including phenols) used in method A include methanol, ethanol,
n-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol,
Examples include hexanol, octanol, phenol, benzyl alcohol, and mixtures thereof. The poly(or oligo)hydrosiloxane used as a raw material in Method A and Method B has the general formula The one expressed as is usually used. In addition to this,
For example, the general expression Cyclic oligomers of the form can also be used. R
Although methyl, ethyl, phenyl, etc. can be used, methyl is usually used. The poly(or oligo)hydrosiloxane mentioned above can have various viscosities, but those having a viscosity of 10 to 1000 centistokes at 30°C are preferably used. In addition, when using a hydrocarbon-soluble organomagnesium compound or a complex compound as (A)(ii)(c), if you use exactly the same as that already explained in (A)(ii)(a), good. Further, when an organic boron compound is used, for example, triethyl boron, tri-n-butyl boron, triisobutyl boron, etc. can be used, and triethyl boron is particularly preferably used. Next, the organometallic compound used in the present invention (B) will be explained. Examples of the organometallic compound used in the present invention (B) include organoaluminum compounds, organoboron compounds, organozinc compounds, organolithium compounds, hydrocarbon-soluble organomagnesium compounds or complex compounds, such as triethylaluminum, triisobutyl Aluminum, tri-n-hexyl aluminum, tridecyl aluminum,
Diethylaluminium hydride, aluminum isoprenyl, diethylaluminium ethoxide, methylethylhydrosiloxyaluminum diethyl and mixtures thereof, triethylboron, diethylzinc, n-butyllithium, di-n-
Butylmagnesium-triethylaluminum complex compound, n-butyl sec-butylmagnesium,
Examples include n-butylethylmagnesium. Preferred examples include organoaluminum compounds and hydrocarbon-soluble organomagnesium compounds. Next, catalyst synthesis will be explained. First, (A)(i)
A description will be given of obtaining a hydrocarbon-insoluble solid by reacting the hydrocarbon-soluble organomagnesium compound or complex compound (a) with the chlorosilane compound (b). The reaction is carried out in an inert hydrocarbon medium, such as aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, or ethers, tetrahydrofuran, etc. The reaction can be carried out in an ether type medium or a mixed medium thereof. From the viewpoint of catalytic performance, an aliphatic hydrocarbon medium is preferably used. Although there is no particular restriction on the reaction temperature, it is preferably carried out at 40° C. or higher in view of the progress of the reaction. There is no particular restriction on the reaction ratio of the two components, but preferably the chlorosilane component is added to 1 mole of the organomagnesium component.
0.01 mol to 100 mol, particularly preferably 0.1 mol to 10
A molar range is recommended. Regarding the reaction method, there is a simultaneous addition method in which two types of catalyst components are simultaneously introduced into the reaction zone and reacted, or one type of catalyst component is charged into the reaction zone in advance, and then the remaining one type of catalyst component is introduced into the reaction zone. react while doing so. Both so-called forward (reverse) addition methods are possible and give favorable results. Next, a method for preparing solid component (i) consisting of the hydrocarbon-insoluble solid obtained by the above reaction and (c) a halogen atom-containing titanium or vanadium compound will be explained. There are no particular limitations on this preparation method, and various commonly used supporting methods can be used. For example, the method described in Japanese Patent Publication No. 56-43046 by the present applicant,
That is, for example, a method of reacting and supporting the solid with titanium tetrachloride in an inert hydrocarbon solvent such as heptane, hexane, cyclohexane, etc., or a method disclosed in Japanese Patent Application Laid-Open Nos. 60-4505 and 60-4506 by the present applicant. etc., that is, a method in which the solid is once reacted with alcohol, aldehyde, etc., and then a titanium compound such as titanium tetrachloride is supported while being reduced with an organoaluminum compound such as diethylaluminum chloride. Can be done. Next, supporting of the chromium compound in (A)(ii) will be explained. The chromium compound can be supported on the inorganic oxide support by known methods such as impregnation, solvent distillation, and sublimation deposition. Depending on the type of chromium compound, it may be supported by an appropriate method, either aqueous or non-aqueous. For example, chromium trioxide,
When using chromium acetate, water may be used, and when using chromium acetylacetonate, a non-aqueous solvent such as toluene may be used. The amount of chromium supported is
0.05 in weight percent of chromium atoms to support
~5%, preferably 0.2-2%. Next, firing activation of the supported solid in (A)(ii) will be explained. Firing activation is generally carried out in the presence of oxygen in a non-reducing atmosphere, but it can also be carried out under an inert gas or reduced pressure. Preferably, air substantially free of moisture is used. Firing temperature is 300
C. or higher, preferably 400 to 900.degree. C. for several minutes to several tens of hours, preferably 30 minutes to 10 hours. During firing, it is recommended to blow in sufficient dry air and activate firing under a fluidized state. Of course, it is also possible to use a known method in which fluorine-containing salts are added at the time of supporting or firing to adjust the activity, molecular weight, etc. Next, the calcined activated solid in (A)(ii) and (ii)
solid component (ii) by reaction with the organometallic compound of (c)
Explain how to obtain. The reaction is carried out in an inert hydrocarbon medium, such as aliphatic hydrocarbons such as hexane, heptane, cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, or a mixture thereof. It can be done with There is no particular restriction on the reaction temperature, for example, room temperature to 100℃
It can be carried out at customary temperatures between . The reaction ratio of the two components is 0.05 to 50 moles of the organometallic component per mole of the chromium component in the solid, especially 0.5
A range of ˜10 moles is preferably used. As for the reaction method, a method is used in which a chromium component is charged in advance in a reaction zone and then the organometallic compound is introduced while reacting, or a method in which a part or all of the organometallic compound is charged in advance and a chromium component is introduced. Next, a method for obtaining the catalyst solid component (A) by mixing the solid component (i) obtained in (A)(i) and the solid component (ii) obtained in (A)(ii) will be described. As for the method of mixing, solid components
Method of introducing (i) into solid component (ii) or solid component
Any method of introducing (ii) into solid component (i) can be used, and the mixing can be carried out either in the presence or absence of an inert hydrocarbon medium, but preferably an inert hydrocarbon medium. It is carried out in the presence of hydrogen medium. The ratio of each component to be combined is from 0.001 to solid component (i)/solid component (ii) weight ratio.
10, preferably in the range of 0.005 to 1.
There are no particular restrictions on the mixing temperature, for example room temperature to 100%
It can be carried out at customary temperatures between . Next, a method of combining the catalyst solid component (A) obtained by mixing and the organometallic compound (B) will be explained. The catalyst solid component (A) and the organometallic compound (B) may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. It is also possible to use a method in which the catalyst solid component is previously treated with the organometallic compound and then further combined with the organometallic compound and fed into the polymerization system. The ratio of both components to be combined is (organic metal)/(Cr+Ti
+V) molar ratio of 0.01 to 3000, preferably 0.1 to 3000
A range of 100 is recommended. Next, a method for polymerizing olefin using the catalyst of the present invention will be explained. Olefins which can be polymerized using the catalysts of the invention are alpha-olefins, especially ethylene. Furthermore, the catalyst of the present invention can also be used for copolymerization of ethylene with monoolefins such as propylene, butene-1, hexene-1, etc., or for polymerization in the coexistence of dienes such as butadiene, isoprene, etc. By carrying out copolymerization using the catalyst of the present invention, it is possible to produce polymers with a density in the range of 0.91 to 0.97 g/cm ³ . As the polymerization method, usual suspension polymerization, solution polymerization, and gas phase polymerization are possible. In the case of suspension polymerization or solution polymerization, the catalyst is a polymerization solvent such as propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into the reactor under an inert atmosphere. By pressurizing ethylene at 1 to 200 kg/cm ² to the bottom, polymerization can be carried out at a temperature of room temperature to 320°C. In addition, a so-called high-pressure polymerization method in which polymerization is carried out using a tubular reactor, an autoclave reactor, an autoclave to a tubular reactor, etc. at a pressure of 200 to 2000 Kg/cm ² and a temperature of 150 to 300°C may also be applied. is possible. On the other hand, in gas phase polymerization, ethylene is heated at a pressure of 1 to 50 kg/cm ² at a temperature of room temperature to 120°C, using a fluidized bed, moving bed, etc. to ensure good contact between ethylene and the catalyst.
Alternatively, polymerization can be carried out by mixing by stirring or the like. The catalyst of the present invention has high performance, 80℃, 10Kg/cm ²
It shows sufficiently high activity even under relatively low temperature and low pressure polymerization conditions. In this case, since the produced polymer exists in the polymerization system in a slurry state, the increase in viscosity of the polymerization system is extremely small. Therefore,
The polymer concentration in the polymerization system can be increased to over 30%, resulting in high production efficiency. Furthermore, due to its high activity, the step of removing catalyst residue from the produced polymer can be omitted. The polymerization may be carried out in a conventional one-stage polymerization using one reaction zone, or using multiple reaction zones.
It may also be carried out by so-called multi-stage polymerization. The polymer polymerized using the catalyst of the present invention has a wide molecular weight distribution even in ordinary one-stage polymerization, and is extremely suitable for blow molding and extrusion molding applications. Multi-stage polymerization in which polymerization is carried out under two or more different reaction conditions makes it possible to produce polymers with a wider molecular weight distribution. In order to adjust the molecular weight of the polymer, it is of course possible to use known techniques such as adjusting the polymerization temperature, adding hydrogen to the polymerization system, or adding an organometallic compound that tends to cause chain transfer. Furthermore, it is also possible to perform polymerization by combining methods such as adding a titanate ester to control density and molecular weight. (Effects of the Invention) If the method of the present invention is used in which the Phillips catalyst side is reacted with a specific organometallic compound and then mixed with the Ziegler catalyst for polymerization, as is clear from the Examples and Comparative Examples described below, both The activity is much higher than that of simple mixing or co-pulverization by ball milling. Furthermore, it is possible to obtain a polymer that is highly active even in the region where the Phillips catalyst is large, has a wide molecular weight distribution, and has fluidity suitable for blow molding and extrusion molding. Further, complicated catalyst synthesis operations such as co-pulverization are not required. (Examples) Examples of the present invention will be shown below, but the present invention is not limited to these Examples in any way. In addition, the catalytic activity in the examples refers to the monomer pressure.
At 10Kg/cm ² , it represents the amount of polymer produced (g) per 1g of catalyst solid component per hour. Also, MI
stands for melt index, ASTM D-
1238, measured at a temperature of 190°C and a load of 2.16 kg. FR has a temperature of 190℃ and a load of 21.6Kg.
It is the quotient obtained by dividing the value measured by MI by MI, and is known to those skilled in the art as an index representing the breadth of molecular weight distribution. Example 1 (1) Synthesis of catalyst solid component (A) (1-1) Synthesis of hydrocarbon-insoluble solid 27.6 g of di-n-butylmagnesium and 3.8 g of triethylaluminum were mixed together with 200 ml of heptane at a temperature of 500 g.
An organic magnesium complex solution was obtained by placing the mixture in a nitrogen-substituted flask and reacting at 80°C for 2 hours. On the other hand, oxygen and moisture inside a 500 ml flask equipped with a dropping funnel and a water-cooled reflux condenser were removed by dry nitrogen replacement, and a 1 mol/l heptane solution of trichlorosilane (HSiCl ₃ 150 mmol) was removed under a nitrogen atmosphere. was charged and the temperature was raised to 50°C. Next, 150 mmol of the above organomagnesium complex solution was weighed into a dropping funnel, added dropwise over 1 hour while stirring at 50°C, and reacted at this temperature for another 1 hour. The resulting hydrocarbon-insoluble white precipitate was isolated, washed with hexane and dried to yield a white basic solid. As a result of analyzing this solid, it was found that Mg was 9.20 mmol per 1 g of solid.
Cl19.20mmol, Si1.70mmol, alkyl group
It contained 0.94 mmol, and the specific surface area measured by BET method was 270 m ² /g. (1-2) Synthesis of solid component (i) In a pressure-resistant container purged with nitrogen, the above basic solid
Add 2.0g and 30ml of titanium tetrachloride and stir.
After reacting at 130° C. for 2 hours, the solid portion was isolated by filtration, thoroughly washed with hexane and dried to obtain pale reddish-purple solid component (i). This solid component
As a result of analyzing (i), it was found that it contained 2.5% by weight of Ti, and the specific surface area measured by BET method was 210m ² /
It was hot at g. (1-3) Preparation of supported calcined solid Dissolve 0.4 g of chromium trioxide in 80 ml of distilled water, and add silica (Fuji Davison Grade 952) to this solution.
20g was immersed and stirred at room temperature for 1 hour. This slurry was heated to distill off the water and then heated to 120°C.
Drying was carried out under reduced pressure for 10 hours. This solid was calcined at 800° C. for 5 hours under dry air circulation to obtain a supported calcined solid. The resulting supported calcined solid contained 1% by weight of chromium and was stored at room temperature under a nitrogen atmosphere. (1-4) Synthesis of organoaluminium components (A)(ii)(c) 100 mmol of triethylaluminum, 50 mmol of methylhydropolysiloxane (viscosity at 30°C: 30 centistokes) (based on Si), n-heptane
Weigh out 150ml into a glass pressure container under a nitrogen atmosphere,
Al( _{C 2} H ₅ ) _2.5 (OSi・H・CH ₃・
A C ₂ H ₅ ) _{0.5 heptane} solution was synthesized. Then this solution
Weigh out 100 mmol (Al standard) into a 200 ml flask under nitrogen atmosphere, and add 50 mmol of ethanol from the dropping funnel.
A mixed solution of 50 ml of Al
(C ₂ H ₅ ) _{2.0 (OC 2 H 5 ) 0.5 ( OSi ・ H}・CH ₃・C _{2 H 5} ) _0.5
A heptane solution was synthesized. (1-5) Synthesis of solid component (ii) Al(C ₂ H ₅ ) _2.0 ( _{OC 2} H ₅ ) _0.5 (OSi・_H・
_CH3・_C2H5 ) _0.5 heptane _solution 5.7mmol ( _Al standard)
The mixture was weighed into a 300 ml flask equipped with a magnetic induction stirrer under a nitrogen atmosphere, and the total volume was made up to 200 ml with dehydrated and deoxygenated n-heptane. To this stirred solution (1-3)
Weighed out 10 g of the supported calcined solid obtained in
Add at room temperature and stir for 1 hour to react to form solid component (ii)
A suspension containing was obtained. (1-6) Synthesis of catalyst solid component (A) To the suspension containing 10 g of solid component (ii) obtained above, 1 g of solid component (i) was added under nitrogen atmosphere with stirring at room temperature,
A suspension containing the catalyst solid component (A) was obtained. (2) Polymerization A suspension containing 20 mg of the solid component (A) synthesized in (1),
0.05 mmol of diethylaluminium ethoxide as the organometallic compound (B) and 0.8 mmol of dehydrated and deoxygenated hexane were placed in a 1.5-sized autoclave whose interior was vacuum degassed and replaced with nitrogen. The internal temperature of the autoclave was maintained at 80°C, ethylene was added at 10 kg/cm ² , and hydrogen was added to bring the total pressure to 14 kg/cm ² . Polymerization was carried out for 1 hour while maintaining the total pressure at 14 kg/cm ² by replenishing ethylene to obtain 98 g of polymer. Catalytic activity is 4900g polymer/gSolid・hr,
The polymer had an MI of 0.72 and an FR of 82. Comparative Example 1 The chromium-supported calcined solid component in (1-5) of Example 1 and Al(C ₂ H _{5 ) 2.0 (} OC _{2 H 5} ) _0.5 (OSi・H・
The reaction with CH ₃・C ₂ H ₅ ) _0.5 was omitted, and the chromium-supported calcined solid component _obtained in (1-3) was used as it was as solid component (ii), and the rest was the same as in Example 1. Synthesis and polymerization were carried out. Polymer yield is
50g, catalyst activity is 2500, MI0.52, FR70,
Compared to Example 1, the catalyst activity, MI, and FR were all lower. Comparative Example 2 Solid component (i) obtained in Example 1 (1-2)
0.4 g and 4.0 g of the chromium-supported calcined solid component obtained in (1-3) of Example 1 (that is, the one that has not been reacted with the organometallic component of (1-5)) were placed in a 9 mm diameter stainless steel plate. Internal volume containing 25 balls
The mixture was charged into a 100 cm ³ stainless steel ball mill under a nitrogen atmosphere and co-pulverized for 5 hours in a vibrating ball mill at 1000 vib./min. to obtain a catalyst solid component (A).
Using this heptane suspension of the catalyst solid component (A), polymerization was carried out in the same manner as in Example 1 (this is the catalyst described in JP-A-59-168001, which is the prior art). . The results showed that the polymer yield was 56 g, the catalytic activity was 2800, the MI was 0.71, and the FR was 81, which was lower than in Example 1.

【table】

【table】

【table】

【table】

[Table] Examples 2 to 7 The raw materials and compositions of solid components (i) and (ii) and the types and amounts of organometallic compounds (A), (ii), (c), and (B) in Example 1 were changed, and others. All experiments were carried out in the same manner as in Example 1, the conditions are listed in Tables 1, 2 and 3, and the results shown in Table 4 were obtained. Example 8 The synthesis of solid component (i) was changed as follows, and the other synthesis and polymerization were carried out in the same manner as in Example 1.
That is, in the synthesis of solid component (i), Example-1
A suspension containing 10 g of the solid obtained in the same manner as in (1-1) Synthesis of hydrocarbon-insoluble solid was mixed with 50 mmol of butyl alcohol and 300 ml of n-hexane.
The reaction was carried out at 80° C. for 1 hour with stirring, the supernatant was removed by decantation, and the mixture was further washed twice with 300 ml of n-hexane. This slurry was kept at 10℃ and titanium tetrachloride was added.
10mmol and ethylaluminum sesquichloride
After introducing 11 mmol and reacting for 30 minutes with stirring,
The temperature was raised to 60°C, the reaction was carried out for 2 hours, and after cooling, the supernatant was removed by decanting, and the mixture was further washed twice with 300 ml of hexane, and further 300 ml of heptane was added to obtain a suspension of solid component (i). Ta. (Titanium contained in 1 g of solid was 24% by weight.) Using this, the catalyst solid component (A) was synthesized and polymerized to obtain 100 g of polymer. Catalyst activity is 5000g polymer/gSolid・Hr, polymer MI0.80, FR80
It was hot. Comparative Example 3 _Chromium -supported calcined solid component in solid component (ii) of Example 8 and Al(C ₂ H _{5 ) 2.0 (} OC ₂ H ₅ ) _0.5 (OSi・H・
By omitting _the reaction with CH ₃・C ₂ H ₅ ) _0.5 and using the chromium-supported calcined solid component as it is as solid component (ii),
The synthesis and polymerization were otherwise carried out in the same manner as in Example 8. Polymer yield 45g, catalyst activity 2250,
The MI was 0.48 and the FR was 72, and the catalyst activity, MI, and FR were all lower than those in Examples.

[Brief explanation of the drawing]

FIG. 1 is a schematic flowchart illustrating aspects of the present invention.

Claims (1)

[Scope of Claims] 1 (A) (i) A hydrocarbon-insoluble solid obtained by the reaction of (a) a hydrocarbon-soluble organomagnesium compound or complex compound and (b) a chlorosilane compound containing an Si-H bond; c) A solid component consisting of a titanium or vanadium compound containing a halogen atom.
(i) and (ii) (a) chromium compound supported on (b) inorganic oxide support.
Using a catalyst consisting of a catalyst solid component (A) obtained by mixing the solid obtained by firing with (c) a solid component (ii) reacted with an organometallic compound, and (B) an organometallic compound. A method for polymerizing olefin, characterized by: 2 (i) The hydrocarbon-soluble organomagnesium compound or complex compound in (a) has the general formula M〓Mg〓R ¹ _p R ² _q X _r Y _s
(In the formula, α is 0 or a number larger than 0, β is a number larger than 0, p, q, r, s are 0 or a number larger than 0, and have the relationship p+q+r+s=mα+2β, M is aluminum, zinc , boron, beryllium, and lithium, m represents the valence of M, R ¹ and R ² are hydrocarbon groups having the same or different numbers of carbon atoms, and X and Y are the same or different groups. , OR ³ , OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹
R ³ and R ⁹ are hydrocarbon groups, R ⁴ is
R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom or a hydrocarbon group. Containing chlorosilane compounds
The polymerization method according to claim 1 or 2, wherein HSiCl ₃ or HSiCl ₂ CH ₃ is used. 4. The polymerization method according to any one of claims 1 to 3, wherein the chromium compound in (ii)(a) is chromium trioxide or a compound that at least partially forms chromium oxide upon calcination. . 5. The polymerization method according to any one of claims 1 to 4, wherein the inorganic oxide carrier in (ii)(b) is silica. 6 (ii)(c) The organometallic compound has the general formula AlR ¹⁰ _x
(OR ¹¹ ) _y (OSiHR ¹² R ¹³ ) _z (where x≧1, 2≧
y≧0, 2≧z≧0, and x+y+z=3, and R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different hydrocarbon groups having 1 to 20 carbon atoms) Aluminum compound, or general formula M〓Mg〓
_R ¹ _{p R} ² _q
2β relationship, M is an atom selected from aluminum, zinc, boron, beryllium, and lithium, m represents the valence of M, and R ¹ and R ² are hydrocarbon groups having the same or different numbers of carbon atoms. , X and Y are the same or different groups, OR ³ ,
OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ represents a group, R ³ ,
A patent for a hydrocarbon-soluble organomagnesium compound or complex compound or organoboron compound represented by R ⁹ is a hydrocarbon group and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms or hydrocarbon groups. A polymerization method according to any one of claims 1 to 5. 7. The polymerization method according to any one of claims 1 to 6, wherein the organometallic compound (B) is an organoaluminum compound, a hydrocarbon-soluble organomagnesium compound, or an organoboron compound.