JPS62116608A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a polymer having a wide MW distribution, excellent flow, etc., by polymerizing an olefin by using a highly active catalyst comprising a catalyst solid component obtained by mixing specified two solid components and an organometallic compound. CONSTITUTION:A solid component (A) obtained by a reaction of a hydrocarbon- soluble organomagnesium compound or complex compound (e.g, formula I) with a halogen-containing titanium or vanadium compound (e.g., TiCl4) is mixed with a solid component (B) obtained by allowing an inorganic oxide support to support a chromium compound (e.g, CrO3), calcining this support and reacting the calcined support with an organometallic compound (e.g., formula II). An olefin (e.g., ethylene) is polymerized by using a catalyst comprising the obtained catalyst solid component and an organometallic compound (e.g., diethyl-aluminum ethoxide) to obtain an olefin polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for polymerizing olefins, particularly ethylene or ethylene and other 1-olefins. Specifically, it is a novel, highly active catalyst that uses a solid catalyst component that is a mixture of a specific titanium- or vanadium-containing magnesium compound and a chromium-containing solid reacted with a specific organometallic compound. This invention relates to an olefin polymerization method that yields a wide variety of polymers.

(Prior Art) Olefins, especially ethylene or ethylene and other 1-
In polymerization with olefins, a technology that simultaneously uses a Ziegler type catalyst containing titanium, nonadium, or a mixture thereof and a Phillips type catalyst containing a chromium compound as an inorganic oxide is a technology to obtain a polymer with a wide molecular weight distribution. Are known. Specifically, a technique for blending the two is disclosed in JP-A-57-139102, and a technique for using both by zeal milling is disclosed in JP-A-59-1989.
It is publicly known in JP 168001 and JP 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, and has a wide molecular weight distribution and fluidity suitable for blow molding and extrusion molding. There is.

However, the catalyst device requires complicated operations such as co-pulverization, and since the Phillips catalyst is a strongly oxidizing substance, it poisons the Ziegler catalyst when mixed, and the Phillips catalyst has a wide molecular weight distribution. There was a problem that sufficient activity could not be obtained in areas with a large amount of .

(Means for Solving the Problems) As a result of repeated research to solve the above problems, the present inventors discovered that the Phillips catalyst side was reacted with a specific organometallic compound before being mixed with the Ziegler catalyst. by doing,
It was discovered that a polymer with high activity and a wide molecular weight distribution can be obtained, and the present invention was achieved.

That is, the present invention provides (4) (i) (,) a hydrocarbon-soluble organomagnesium compound or complex compound obtained by the reaction with (b) a titanium or Nonosu-crumb compound containing at least one halogen atom. Solid component (i) and (ii) (
a) a chromium compound supported on (b) an inorganic oxide carrier and a solid obtained by firing, and (c) a solid component (i1) obtained by reacting with an organometallic compound; (B) An olefin polymerization method characterized by using a catalyst comprising an organometallic compound.

The present invention will be explained in detail below.

The hydrocarbon-soluble organomagnesium compound or complex compound used in the present invention (4)(i)(a) has the general formula MaMg, R'R2qX, Y, (wherein α is o or a number larger than o, β is a number greater than O, p, q, r
, s is 0 or a number larger than 0, p+q+r+s=mg
+2,5, M is an atom selected from aluminum, zinc, boron, beryllium, and lithium, m represents the valence of M, and R1 and R2 are hydrocarbon groups having the same or different numbers of carbon atoms. , X, Y are the same or different Natsuta groups, OR4, 08iR'R5R4, NR'
R4, SR' represents a group, R3 and R9 are hydrocarbon groups, R4, 几s, R'.

R7, BS represents a hydrogen atom or a hydrocarbon group). Preferably, M is aluminum, and X and Y are OR' or 08iR'R5R'.

β/α above 1. It is recommended that (r+3)/(α+β)≦1. The synthesis of these hydrocarbon-soluble organomagnesium compounds or complex compounds is generally known, and may be performed, for example, according to the publications, publications, publications, etc. listed below. That is, those in which M is aluminum and α〉O are disclosed in JP-A-50-139885, JP-A-48-18235, JP-A-47-24009, Annalen der Hiemi Vol. 605, pp. 93-97 ( i957), JP-A-50-154388, JP-A-50-157490, JP-A-53-4069
It may be synthesized from the corresponding organomagnesium and organoaluminum with reference to Publication No. 6, and M is zinc, boron,
Beryllium etc. with α〉0 are JP-A-50-1507
No. 86, JP-A-51-97687, JP-A-Sho 5
It may be synthesized from corresponding organomagnesium, organozinc, etc. with reference to JP-A No. 1-107384 and JP-A-52-71421. Further, those with α=0 that are soluble in hydrocarbons include, for example, n-butyl ethylmagnesium, n-butyl 5ee-butylmagnesium, n-butyl 1so-propylmagnesium, etc.
No. 7, JP-A-56-26893, US Pat. No. 4,127,507, US Pat. No. 3,646,231, US Pat. No. 3,766,280, Journal Oshi Organic Chemistry Vol. 34, 1116-
1121 pages (i969), Journal of Organometallic Chemistry Vol. 64, pp. 25-40 (i97
It can be synthesized by referring to 4th year) and using the corresponding Gu IJ Niya compound or alkyl lithium compound.

Examples of the titanium or non-nadium compound containing at least one non-rogen atom used in the present invention (4)(i)(b) include titanium tetrachloride, titanium tetrabromide, ethoxybutane trichloride, butoxytitanium One or a mixture of halides, oxyhalides, and alkoxyhalides of titanium and nonadium, such as trichloride, dibutoxytitanium dichloride P1 tetrachloride, S sodium, and nonadium oxytrichloride, is used. A compound containing three or more halogens is preferred, and tetra-titanium chloride is particularly preferred.

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, nitrate, acetic acid. salts, sulfates, oxalates, alcolades, etc., specifically chromium trioxide, chromyl chloride, potassium dichromate, ammonium chromate, chromium nitrate, chromium acetate, chromium acetylacetonate, ditertiary butylchromate. etc. Chromium dioxide, 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 (4) (A) and (c) will be explained. Examples of organometallic compounds include organoaluminum compounds, organoboron compounds, organozinc compounds,
Examples include organolithium compounds, hydrocarbon-soluble organomagnesium compounds, complex compounds, etc., and preferably,
Examples include organoaluminum compounds, hydrocarbon-soluble organomagnesium compounds or complex compounds, and organoboron compounds. Particularly preferably, the general formula AλR”x(OR”
)y (O8r-H-R1"・B13).

Examples include organoaluminum compounds containing both an alkoxy group and a hydroxyloxy group, and this compound will be described below.

In the above formula, BIG, 几11. R12 and RI3 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 P-decyl, cycloalkyl groups such as cyclohexyl and methylcyclohexyl, and aryl groups such as phenyl, preferably having 2 to 2 carbon atoms. 10 alkyl groups.

Regarding “+Yr”, x + y+z = 3, υ,
The range of X≧1.2≧y≧0, 2≧z≧0 is used.

Preferably X≧1.5, 1.5≧y≧0.25.

The range is 1.5≧z≧0.15 and 1.5≧y+z≧0.5, and particularly preferably X≧z. 1≧y≧0.
5, the range of 1≧z≧0.25 and 1≧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,) Real-alkylaluminium or dialkyl-aluminum Hi-P Li-P and poly(or Ori:P)
) A hydrosiloxy group-containing organoaluminum compound obtained by reacting a hydrosiloxane in a desired ratio is quantitatively reacted with an alcohol (including phenol) to introduce an OR group.

Method B, OR of dialkyl aluminum alkoxide etc.
A group-containing organoaluminum compound is reacted with a poly(or oligo)hydrosiloxane in a desired amount ratio to introduce hydrosiloxy groups.

Regarding the first stage of method A, the present applicant's Japanese Patent Publication No. 46-4
No. 0334 and US Pat. No. 3,661,878, which are described in detail together with NMR and spectra of the reactants, are 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 Person or Method B include trimethylaluminum, triethylaluminum, tri-n-probylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, triethylaluminum, and trimethylaluminum. Examples include phenylaluminum, diethylaluminium ethoxy P1 diethylaluminium n-butoxide, diisobutylaluminum ethoxide, and mixtures thereof.

Alcohols (including phenol) used in Method A include methanol, ethanol, n-propanol, n-butanol, Iso-butanol, 5ec-
Mention may be made of butanol, tert-butanol, hexanol, octatool, phenol, Randyl alcohol, and mixtures thereof.

The poly(or oligo)hydrosiloxane used as a raw material in Method B and method B are generally those represented by the following formulas. In addition, for example, cyclic oligomers having the general formula can also be used. As R, methyl, ethyl, phenyl, etc. can be used, but methyl is usually used. The above poly(
Hydrosiloxanes of various viscosities can be used, but those with a viscosity of 1
0 to 1000 centistokes are preferably used.

In addition, when using a hydrocarbon-soluble organomagnesium compound or a complex compound as (4) (ii) (c), the same compound as that already explained in (4) (A) (,) can be used. 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 () of the present invention will be explained.

Examples of the organometallic compound used in () of the present invention include organoaluminum compounds, organoboron compounds, organozinc compounds, organolithium compounds, hydrocarbon-soluble organomagnesium compounds or complex compounds, such as triethylaluminum, triisobutylaluminum, etc. ,
Tri-n-hexylaluminum, tridecylaluminum, soethylaluminum hydride r1 aluminum imprenyl, diethylaluminum ethoxy P1
Examples include methylethylhyrosiloxyaluminum jetyl and mixtures thereof, triethylboron, diethylzinc, n-butyllithium, dibutylmagnesium-triethylaluminum complex, n-butyl5ec-butylmagnesium, n-butylethylmagnesium, and the like. Preferred examples include organoaluminum compounds and hydrocarbon-soluble organomagnesium compounds.

Next, catalyst synthesis will be explained. First, (A) (i)
The solid component (+) is formed by the reaction between the hydrocarbon-soluble organomagnesium compound or complex compound of (,) and the rogen-containing titanium (or) sodium) compound of (b).
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. However, it is preferably carried out in an aliphatic or alicyclic hydrocarbon. The reaction temperature is preferably below 100°C, particularly preferably below 50°C.

The reaction ratio of the two components is titanium (or) sodium)
Component (i)) 0.0 per mole of organometallic component (a)
A range of 5 to 50 mol, particularly 0.2 to 10 mol, is preferably used. Regarding the reaction method, there is a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted, or a so-called direct addition method in which one catalyst component is charged into the reaction zone in advance and the remaining one component is introduced and reacted. Either (reverse) addition method can be used.

Next, supporting the chromium compound in (4)(i1) will be explained. A chromium compound is supported on an inorganic oxide carrier.

This can be achieved by known methods such as impregnation, solvent distillation, and sublimation deposition. Depending on the type of chromium compound, it may be supported using an appropriate aqueous or non-aqueous method; for example, when using chromium trioxide or chromium acetate, water may be used, and when using chromium acetylacetonate, supporting may be performed using a non-aqueous method such as toluene. A water solvent may be used. The amount of chromium supported is in the range of 0.05 to 5%, preferably 0.2 to 2%, based on the weight nominal of chromium atoms relative to the support.

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. The firing temperature is 300°C or higher, preferably 400°C
~900°C for several minutes to several tens of hours, preferably 3
It is carried out for 0 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 of controlling activity, molecular weight, etc. by adding fluorine-containing salts during supporting or firing.

Next, (A) the calcined activated solid in (A) and (
i1) Obtaining the solid component (ii) by the reaction with the organometallic compound of (c) will be explained. 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, and the reaction can be carried out at a commonly used temperature, for example, between the room temperature and 100°C. The reaction ratio of the two components is preferably in the range of 0.05 to 50 moles, particularly 0.5 to 10 moles of the organometallic component per mole of the chromium component in the solid. 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, solid component (i) obtained in (A) (+) and (A)
A method for obtaining the catalyst solid component (4) by mixing it with the solid component (i1) obtained in (ii) will be explained. As a mixing method, either a method of introducing solid component (i) into solid component (i1) or a method of introducing solid component (i) into solid component (i) can be used. It can be carried out either in the presence or absence of an activated hydrocarbon medium, but is preferably carried out in the presence of an inert hydrocarbon medium.The ratio of both components to be combined is solid component (i)/solid. The weight ratio of component (i1) is 0.
A range of 001 to lO1, preferably o, oos to 1 is recommended. There is no particular restriction on the mixing temperature, for example, room temperature to 1
It can be carried out at customary temperatures between 00°C and 00°C.

Next, a method of combining the catalyst solid component (A) obtained by mixing with the organometallic compound () will be explained.

The solid catalyst component 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 treat the catalyst solid component in advance with the organometallic compound, and then further combine it with the organometallic compound and feed it into the polymerization system. The ratio of both components to be combined is (organometallic)/
The molar ratio of (Or+Ti+V) is 0.01 to 3000
, preferably in the range of 0.1 to 100.

Next, a method for polymerizing olefin using the catalyst of the present invention will be explained.

The olefins that can be polymerized using the catalysts of the invention are alpha-olefins, especially ethylene. Furthermore, the catalyst of the present invention is ethylene, propylene, butene-1, hexene-1
It is also possible to use it for copolymerization with monoolefins such as, or in the presence of dienes such as butadiene and isoprene.

By carrying out copolymerization using the catalyst of the present invention, it is possible to produce a polymer having a density in the range of 0.91 to 0.97 f/m.

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 an aliphatic hydrocarbon such as propane, butane, pentane, hexane, hezotane, -benzene,
Aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane were introduced into a reactor, and ethylene was injected at 1 to 200 vol/1 m2 under an inert atmosphere, and the mixture was heated to room temperature. to 320℃
Polymerization can proceed at a temperature of In addition, using a tubular reactor, an autoclave reactor, an autoclave tubular reactor, etc., a pressure of 200 to 2
It is also possible to apply a so-called high-pressure polymerization method in which polymerization is carried out under conditions of 000 ml/-2 and a temperature of 150 to 300°C.

On the other hand, in gas phase polymerization, ethylene is mixed at a pressure of 1 to 50 Ai7/cm2 at a temperature of room temperature to 120°C using a fluidized bed, moving bed, or stirring to ensure good contact between the ethylene and the catalyst. It is possible to carry out the polymerization using various means.

The catalyst of the present invention has high performance and has a high performance at 80°C and 10 kti/
It exhibits sufficiently high activity even under relatively low temperature and low pressure polymerization conditions of about cm2. 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 30% or more, and the production efficiency is high. 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 in a so-called multi-stage polymerization using a plurality of reaction zones. The polymer polymerized using the catalyst of the present invention has a wide molecular weight distribution even in normal one-stage polymerization,
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.

Adjustment of polymerization temperature to adjust the molecular weight of the polymer,
Of course, it is also possible to use known techniques such as adding hydrogen to the polymerization system or adding an organometallic compound that is likely 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 a Ziegler catalyst for polymerization, the following results can be achieved, as is clear from the Examples and Comparative Examples described below. The activity is much higher than that of a simple mixture of the two. 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. There is also no need for complicated catalyst synthesis membrane operations such as co-pulverization.

(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 monomer pressure of 10 k
g/1wr", represents the polymer production amount (f) of the catalyst solid component 1f/1 hour. Also, MI represents the melt index, and according to A8TM-D-1238, the temperature is 190°C and the load is 2.16A9. FR is the quotient obtained by dividing the value measured at a temperature of 190°C and a load of 21.6 kg by MI, and is known to those skilled in the art as an index representing the breadth of the molecular weight distribution. be.

Example 1 (i) Synthesis of solid component (4) (i-1) Synthesis of solid component (+) Di-n-butylmagnesium 13.89 and triethylaluminum 1.9f were mixed with n-hebutane 2001111 in a volume of 500 d. composition AIMgg(02H5)3 by reacting at 80°C for 2 hours.
A hebutane solution of an organomagnesium complex compound of (n -C!4H9)+2 was obtained. Next, 80 mmol of n-hebutane solution containing 40 mmol (M g + Afl standard) of this organomagnesium complex compound and 40 mmol of titanium tetrachloride were added.
Both components were added dropwise into a 300 rat flask in which water and oxygen had been removed by purging with dry nitrogen, and reacted at -20° C. with stirring for 4 hours. The resulting hydrocarbon-insoluble solid was isolated and washed with n-hebutane. A solid component (D) was obtained.

(i-2) Dissolve 0.42 of the supported calcined solid chromium trioxide in 80 rIL of distilled water,
7 Lika (Fuji Davison Qrade 9) was added to this solution.
52) 20F and stirred at room temperature for 1 hour. This slurry was heated to distill off the water, followed by
It was dried under reduced pressure at 'C 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 in a room under a nitrogen atmosphere.

(i-3) Organic aluminum component (4) (ii)
(c) Synthesis of triethylaluminum 100 mmoj
! , methylhyporobolysiloxane (viscosity at 30°C: 30 centistokes) at 50 mmo°C (based on Si), 150 ml of Q-heptane was weighed into a glass pressure-resistant container under a nitrogen atmosphere, and stirred for 100 min using a magnetic stirrer. ℃
An (c2H3)2. s
(O81-H-OH3.C2H3)0.5 butane solution was synthesized. Next, 100 mmon (g standard) of this solution
was weighed into a 200 mA' flask under a nitrogen atmosphere, and a mixed solution of 50 mmon of ethanol and 5 mmol of ton-heptane was added dropwise from the dropping funnel under water-cooled stirring. (02H5)2. .

(002H5)0.5 (O8i -H-0H3・02
H5) 0.5 butane solution was synthesized.

(i-4) Synthesis of solid component (i1) AN obtained above
(02H5)2.0 (002H5)0.5 (O8
i ・H-CH3・02I (5) 0.5 butane soluble Q
5.7 mmol (based on An) was weighed into a 300 mg 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-hebutane.

To this stirred solution, the supported calcined solid 102 obtained in (i-2) was weighed and added at room temperature under a nitrogen atmosphere, and the mixture was stirred for 1 hour and reacted to obtain a suspension containing the solid component (A). Ta.

(i-S) Synthesis of solid component (4) To the suspension containing 10 y of solid component (ii) obtained above, solid component (i) ISF was added under stirring at room temperature under a nitrogen atmosphere to prepare the catalyst solid component. A suspension containing (4) was obtained.

(2) A suspension containing 20η of the catalyst solid component (4) synthesized in polymerization (i) and 0.05 mmon of diethyl aluminum ethoxide as the organometallic compound (B) were mixed with 0.8 mm of dehydrated and deoxygenated hexane. ℃ and placed in a No. 1,52 autoclave whose interior was vacuum degassed and replaced with nitrogen. Keep the internal temperature of the autoclave at 80℃, and add ethylene at 10A9/cm.
2 was added, and hydrogen was added to bring the total pressure to 14/α2.

By replenishing ethylene, the total pressure was increased to 14 to 9/cm2.
Polymerization was carried out for 1 hour while maintaining the pressure at , to obtain a polymer of 11 fSIF. Catalytic activity is 5800 f polymer/?
The MI of 5olid hrX4 remer was 0.80, and the F value was 79.

Comparative Example The chromium-supported calcined extremely solid component in (i-4) of Example 1 and hfl (c2H3), 6 (002H5)0.
5 (O8i -H-CH3.02H5)6.5 The reaction with 6.5 was omitted, and the chromium-supported calcined solid component obtained in (i-2) was used as it was as solid component (i1), and the rest was the same as in Example 1. Synthesis and polymerization were carried out in the same manner. Polymer yield is 42? , catalytic activity is 2100, MI O,55
, F 68, catalyst activity, MI, compared to Example 1.
Both PRs were low.

Examples 2 to 8 Raw materials and compositions of solid components (i) and (ii) in Example 1 and organometallic compounds (4) (ii) (c),
Example 1 except for changing the type and amount of (B)
The tests were carried out in the same manner as above, and the conditions are listed in Tables 1, 2 and 3, and the results shown in Table 4 were obtained.

Margin below

Claims (1)

[Claims] 1. (A) (i) A solid component obtained by the reaction of (a) a hydrocarbon-soluble organomagnesium compound or complex compound and (b) a titanium or vanadium compound containing at least one halogen atom. (i) and (ii) (a
) A catalytic solid component (A) obtained by mixing a solid obtained by supporting (b) a chromium compound on an inorganic oxide carrier and firing the solid component (c) and a solid component (ii) reacted with an organometallic compound. (B) Olefin polymerization method 2 characterized by using a catalyst consisting of an organometallic compound, (i) The hydrocarbon-soluble organomagnesium compound or complex compound of (a) has the general formula M_αMg_βR^1_
pR ^ 2_q , zinc, boron, beryllium and lithium, m represents the valence of M, R^1, R^2 are hydrocarbon groups having the same or different number of carbon atoms, X, Y are the same or different OR^3, OSiR^4R^5R^6, NR^7R^
8, represents the group SR^9, R^3 and R^9 are hydrocarbon groups, R^4, R^5, R^6, R^7, R^8 represent hydrogen atoms or hydrocarbon groups ), wherein the titanium or vanadium compound of (i) or (b) is a compound containing three or more halogens, or Polymerization method 4 described in Section 2, (ii) (a)
Polymerization method 5 according to any one of claims 1 to 3, wherein the chromium compound in (ii) is chromium trioxide or a compound that at least partially forms chromium oxide upon calcination. Polymerization method 6 according to any one of claims 1 to 4, wherein the inorganic oxide support in b) is silica, the organometallic compound in (ii) and (c) has the general formula AlR
^1^0_x(OR^1^1)_y(OSiHR^1^
2R^1^3)_z (in the formula, x≧1, 2≧y≧0, 2≧
z≧0 and x+y+z=3, R^1^0, R^
1^1, R^1^2 is the same or different number of carbon atoms from 1 to
(representing a hydrocarbon group of 20), or an organoaluminum compound represented by the general formula M_αMg_βR^1_pR^2
_____ Atom selected from zinc, boron, beryllium and lithium, m represents the valence of M, R^1, R^2 are hydrocarbon groups having the same or different number of carbon atoms, X, Y are the same or different is the group and OR
^3, OSiR^4R^5R^6, NR^7R^8, S
Represents a group ^9, R^3 and R^9 are hydrocarbon groups, R
^4, R^5, R^6, R^7, R^8 represent a hydrogen atom or a hydrocarbon group) A hydrocarbon-soluble organomagnesium compound or complex compound or an organoboron compound represented by Polymerization method 7 according to any one of paragraphs 1 to 5, wherein the organometallic compound (B) is an organoaluminum compound, a hydrocarbon-soluble organomagnesium compound, or an organoboron compound, Claim 1 or 6th
The polymerization method described in any one of paragraphs