JPH0341483B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel components of catalysts for the polymerization of alpha-olefins, catalysts prepared therefrom, and especially for the production of ethylene or crystalline copolymers and elastic copolymers of ethylene and alpha-olefin CH ₂ =CHR ( where R is an alkyl group having 1 to 8 carbon atoms). Polymerization of ethylene is carried out using various types of coordination catalysts, one of the most well known being
Titanium or vanadium compounds and the periodic table,
and reaction products with metal-organic compounds of the group. As is known, vanadium catalysts, unlike Ti catalysts, can yield polyethylene having a relatively wide molecular weight distribution (DPM). From French patent 2378047, a component of a catalyst for the polymerization of ethylene is known, which consists of reacting vanadium halogenated compounds with a valence higher than 3 (e.g. VCl ₄ , VOCl ₃ ) with aluminum alkyls in the presence of an ether. Manufactured by _{The reaction product contains or consists essentially of VCl 3 .} The catalyst obtained from the catalyst component by reaction with aluminum alkyl has a relatively high activity, but has a low content of catalyst residue, especially a few ppm.
It is not high enough to produce a polymer with lower residual V content. In practice, polymers containing V in amounts higher than a few ppm are physiologically harmful and the polymers obtained using the catalyst must therefore be subjected to lengthy and expensive purification processes. No. In the field of elastomeric copolymers, the polymerization of ethylene and alpha olefins in the presence or absence of diolefins has to date been carried out using different types of catalysts: the most commonly used are: Hanadium compounds and the periodic table,
and reaction products of metal-organic compounds of group metals. The copolymerization is preferably carried out by using catalysts which are soluble and highly dispersible in the polymerization medium, such as vanadium halides and oxyhalides, vanadium and vanadyl alcoholates and acetylacetonate. By using these catalysts it is possible to obtain essentially amorphous copolymers which in the vulcanized state are characterized by valuable elastic properties. However, the polymer yields for the catalysts used are not high enough to produce polymers with low contents of catalyst residue, especially low contents of residual vanadium. Attempts have been made to avoid this drawback by using activating substances, but even in such cases the yields are always very low and purification of the polymer from the catalyst residue cannot be dispensed with. Therefore, it is possible to obtain ethylene polymers with high activity and containing a sufficient percentage of V to avoid purification of the polymer, while at the same time obtaining a polymer with a broad molecular weight distribution (DPM). It was felt that there was a need to obtain a V-catalyst that could be used. One object of the present invention is to polymerize olefins, in particular ethylene or mixtures thereof with alpha-olefins CH ₂ =CHR, where R is an alkyl group having from 1 to 8 carbon atoms. The purpose of the present invention is to produce a suitable V-based catalyst component which, when used in admixture with aluminum alkyl, can give crystalline copolymers with very low percentages of vanadium; As a result they are physiologically harmless and can also give unsaturated elastic copolymers if saturated elastic copolymers of ethylene and hydrocarbon monomers with more than one double bond are also used. . Polymerization of chlorinated compounds of trivalent vanadium with certain X-ray powder spectra with olefins, in particular ethylene or mixtures thereof with alpha-olefins optionally containing hydrocarbon monomers with more than one double bond. It has now been surprisingly discovered that it can be advantageously used as a component of a solvent. By reaction with the Al metal organic compound, the component forms a catalyst, which is used for the polymerization of ethylene or its mixture with alpha-olefin CH ₂ =CHR, where R is an alkyl group having from 1 to 8 carbon atoms. It is very active in The resulting polymer generally contains catalyst residues in such an amount that a purification step is not required. The catalyst component (component a) forming the object of the present invention has the general formula VCl _o (OR) _n [wherein R is a hydrocarbon group having 1 to 18 carbon atoms, especially a carbon number of 1 to 10]. alkyl, cycloalkyl, aryl or group R _1P Si(OH) _3-P having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, where R ¹ is a hydrocarbon group and 1p3, and n is 1.5 to 3, m is 3-n], and in the spectrum of ordinary VCl ₃ d
The maximum diffraction line appearing at =5.75 Å, d = 2.67 Å and d = 1.74 Å is at least three times the diffraction line appearing at d = 5.75 Å, and d = 2.67 Å and d =
Included are vanadium compounds having an X-ray powder spectrum that exhibits a half-width broadening at least four times that of 1.74 Å or such that the diffraction lines disappear. In the above formula, m+n can also differ slightly from 3, taking into account analytical errors. The expression "ordinary vanadium chloride" is
VCl ₃ having the X-ray analysis spectrum reported in ASTM 15-382. Another object of the invention is to combine the catalyst component (a) with a metal-organic compound (b) of Al, preferably an Al-trialkyl compound or a compound of the general formula [In the formula, M=O, S, N-R, P-R,

[Formula], and R can be a hydrocarbon group having 1 to 18 carbon atoms, especially alkyl or aryl having 1 to 20 carbon atoms, and R' is the same as R or halogen or Alpha-olefin CH ₂ =CHR (where and R has 1 carbon number
-8 alkyl groups). Typical vanadium compounds as catalyst components are VCl ₂ (OC ₄ H ₉ ), VCl _1.5 (OC ₄ H ₉ ) _1.5 ,
VCl ₃ , VCl _2.8 (OC ₂ H ₅ ) _0.2 , VCl ₂ (OC ₆ H ₅ ), VCl ₂
(OC ₈ H ₁₇ ), VCl ₂ [OSi(CH ₃ ) ₃ ], VCl _1.5 , [OSi
(CH ₃ ) ₃ ] _1.5 . Component (a) of the catalyst of the invention can be prepared according to a variety of methods, one preferred method being to add a molar excess of the chlorinated compound of V to an organic compound containing at least one -OH group. It consists of reacting a compound and decomposing the reaction product formed using a compound capable of reacting with the -OH groups of the reaction product to give a compound that is soluble in the reaction medium. The reaction between the chlorinated compound of V and the -OH group-containing organic compound is carried out at 0°C in the presence or absence of a solvent.
and the boiling point of the organic compound containing OH groups, using a molar ratio of V compound to organic compound containing OH groups between 2 and 300. Organic compounds which can be used and which have at least one -OH group are alcohols and thioalcohols, phenols and thiophenols having 6 to 18 carbon atoms and silanols R _1P Si(OH) _4-P [where R ¹ is as defined above] and 1p3]. Alcohols that can be used include those with carbon numbers of 1 to 18.
These are aliphatic alcohols, alicyclic alcohols, and aromatic alcohols. Aliphatic alcohols that can be used include, for example, methyl,
Ethyl, propyl, butyl, hexyl, and octyl alcohol. Alicyclic alcohols that can be used are cyclopentanol and cyclohexanol. Examples of aromatic alcohols are benzyl alcohol, alpha phenyl ethyl alcohol. As phenols, phenols, cresols and substituted phenols can be used. Examples of silanols are trimethylsilanol, triphenylsilanol, butyltrisilanol. A preferred starting V compound is _VCl3 . The decomposition of the products obtained from the reaction between V compounds and organic compounds containing -OH groups can be carried out in the presence of any solubility using halogenated compounds of the group of the periodic table with the above characteristics. , using a molar excess of the halogenated compound at temperatures between 30 and 200<0>C. Examples of halogenating agents are Si, Sn, Sb, B and Al,
It is a compound of Ti and V. Representative examples of such compounds include, for example, Sn or
Si tetrahalide, Cl ₂ Si(CH ₃ ) ₂ , Cl ₃ SiCH ₃ ,
SbCl ₃ , AlCl ₃ , TiCl ₄ , VOCl ₃ , preferred compounds are SnCl ₄ , SiCl ₄ and TiCl ₄ . If the starting vanadium compound has a valence of more than 3, it is possible to use a halogenated compound mixed with a reducing agent or a reducing halogenated compound. Such reducing compounds include, in particular, metal-organic compounds of the group metals of the periodic table, Si, Sn and
It is a compound of Sb, and a halide of Al and B. Some representative examples are Al-alkyl, e.g.
Al-triisobutyl, Al-triethyl, Si-tetraalkyl, Si-alkyl hydrides, polyhydrosiloxanes and also Al(OEt)Et ₂ , Al(i
−C ₄ H ₉ ) ₂ H, etc. Examples of halogenated reducing compounds are halogensilanes, Al-alkyl halides, e.g.
AlR ₂ Cl, AlRCl ₂ , Al ₂ Et ₃ Cl ₃ , Al ₃ Et ₃ Br ₃ , Al
(OEt)EtCl. When using SiCl ₄ as a reagent to decompose the reaction product between a V compound and an organic compound containing an -OH group, a small amount of Si compound, i.e. 0.5-7% by weight as Si, is present in the product. It may remain. When using TiCl ₄ as the halogenated compound for decomposition, products are obtained which are essentially free of OR groups and contain an amount of Ti ranging from 0.5 to 10% by weight. Representative examples of Al metal organic compounds used as component (b) of the catalyst are _: Al( _C2H5 ) ₃ , Al(i- _C4H9 ) ₃ , Al( _{C2H5 ) .} ) ₂ Cl,
Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ , Al(n-C ₃ H ₇ ) ₂ Cl, Al(i-
_C4H9 ) _2H , Al( _C8H17 ) ₃ , _{Al ( C6H13} ) _{3 .} Preference is given to using Al metal-organic compounds containing two or more Al atoms bonded to each other by heteroatoms. Representative examples of such compounds are listed below. ( _H5C2 ) _2Al -O-Al _{( C2H5} ) _{2 ,} (i- _C4H9 ) _{2Al -} O-Al(i- _C4H9 ) _{2 .} Methods for the preparation of these compounds are known from the literature. The ratio between component (b) and component (a) is greater than 1 and generally comprises a wide range, with ratios between 5 and 500 being preferably used. When the catalyst is used to polymerize propylene to produce highly isotactic polymers, component (a) is and component (b) both need to be modified with an electron donor compound. In another refinement of the invention, the starting V compound and -
Component (a) obtained by decomposing a reaction product between OH group-containing organic compounds using a halogenated compound different from the Ti halogenated compound is treated with a liquid halogenated Ti compound under reaction conditions. Then,
It has been found that catalysts can be obtained that give very high yields without affecting the molecular weight distribution (DPM). Examples of Ti compounds used are tetravalent Ti halide compounds, such as TiCl ₄ , TiBr ₄ and Ti halogen-alcoholates. The reaction with the Ti compound is preferably carried out using an excess amount of liquid Ti.
The unreacted compounds are then separated. If _TiCl4 is used as reagent and reaction medium, the reaction temperature is generally between 50<0>C and the boiling point of _TiCl4 , especially between 80<0>C and 135<0>C. Catalyst components of the present invention may be used, for example, in the British patent
1292853, e.g. silica, alumina, activated form of Mg
It can also be supported on a carrier such as a halide,
Alternatively, it can be diluted with an inert solid substance. The catalyst obtained therefrom is prepared according to known techniques.
Used in the (co)polymerization of ethylene and alpha olefins in the gas phase or in the liquid phase optionally containing hydrocarbon solvents. Examples of solvents are propane, butane, hexane, heptane and cyclohexane. For ethylene polymerization, it is generally at a pressure below 50 atmospheres and at a temperature below 150°C, or at a pressure above 10 atmospheres and
Operated at temperatures ranging from 150° to 300°C. A crystalline copolymer of ethylene is obtained containing an ethylene polymer having a density greater than 0.95 g/cm ³ and up to about 10 mole % alpha olefin having a density in the range of 0.91 to 0.95 g/cm ³ . , they have good mechanical properties and a particularly broad molecular weight distribution (M _W /M _o >10). Alpha olefins for obtaining an elastomeric polymer of ethylene include propylene, butene-1,
4-Methylpentene-1 can be used. Diolefins include butadiene-1,3, isoprene, hexadiene-1,4, dicyclopentadiene, decatriene-1,4,9,4-vinylcyclohexene, cyclooctadiene-1,5
can be used. The ethylene content in the binary copolymer is generally 20~
It is in the range of 80% by weight. The content of the third monomer (diene or polyene) in the unsaturated copolymer ranges from 0.1 to 20 mol%. The copolymerization is carried out according to known techniques, in particular it is carried out in the liquid phase, optionally in the presence of an inert hydrocarbon solvent. It can be carried out at temperatures below 150°C, preferably below 60°C. Polymerization of alpha olefins (eg propylene) is carried out according to the known techniques mentioned above. Polymerization temperature is 50°C to 150°C, preferably 40° to 90°C,
range, and is carried out at or above atmospheric pressure. The following examples are given merely to illustrate the invention and are not intended to limit it. Preparation Examples 1 to 7 of Catalyst Component (a) Various catalyst components, both for the polymerization of ethylene and for the copolymerization of ethylene and alpha olefin, were prepared by the following procedure: 4.07 g of powder Anhydrous VCl ₃ was dissolved in 50 ml of absolute alcohol under N ₂ atmosphere in a glass container with a magnetic stirrer. The resulting solution was evaporated to dryness until a solid product was obtained. The solid product thus obtained was decomposed using 200 ml of SiCl ₄ and
And it was kept under reflux for 48 hours. In Example 5, instead of _SiCl4 , an equimolar amount of
Cl ₃ SiCH ₃ was used as a decomposition agent for the reaction product between VCl ₃ and alcohol. In Examples 6 and 7, equimolar amounts of TiCl ₄ were used instead of SiCl ₄ (double treatment over 2 hours at 130° C.). The resulting purple solid was isolated by filtration and washed repeatedly with 50 c.c. of anhydrous n-heptane each time, and finally it was washed under vacuum (0.5 mmHg) for 20
Dry for at least 1 hour at <0>C. In all examples, the final product obtained essentially has the general formula VCl _o (OR) _n , where n and m
1.5 to 3] and contained varying amounts of Si or Ti, depending on the reagents used. The X-ray analysis spectra of the products of Examples 6 and 7 show that d=5.75 in the powder spectrum of ordinary VCl ₃
Å, the half-width spread of the maximum intensity line appearing at d=2.67 Å and d=1.74 Å is shown. The X-ray analysis spectra of the products of Examples 1 to 5 were characterized by the fact that they did not exhibit the line of maximum intensity appearing at the above values in the spectrum of ordinary VCl ₃ . Example 8 5.3 g of the catalyst component prepared as in Examples 1 to 5 was added to 100 ml of the catalyst at 130° C. for 2 hours.
Treated with _TiCl4 . TiCl ₄ was removed by filtration at 130°C and an equal amount of it was added and reacted for 2 hours at the same temperature, which was filtered at 130°C to remove TiCl ₄
until the chlorine ions in the liquid disappear.
Washed with n-heptane at 90°C. The elemental analysis of the solid product dried in vacuo is reported in the table. The spectra of the X-ray analysis are of the type of Examples 6-7.

Table Example 9 3.5 g of anhydrous powdered MgCl ₂ and 8.1 g of anhydrous powdered VCl ₃ were dissolved in 150 ml of anhydrous C ₂ H ₅ OH at room temperature in a container with a magnetic stirrer.
The resulting solution was evaporated to dryness until a green solid product was obtained. The solid product thus obtained was treated with 200 ml of _TiCl4 . Then set the temperature to 110
℃ and held at that level for 2 hours. The resulting purple solid was isolated by filtration, and it was
It was treated again with 400 c.c. of TiCl ₄ for 2 hours at a temperature of 135°C. It was washed with n-hepta until the chlorine ions in the solution disappeared. The elemental analysis of the dried solids is reported in the table. Example 10 7.8 g each of VCl ₃ , 3.4 g MgCl ₂ and 100
Example 9 was repeated using ml _{of C2H5OH} . The solid product obtained by the method according to Example 9 was
ml of SiCl ₄ at reflux for 48 hours. It was filtered and the solid product formed was washed repeatedly with n-heptane. The elemental analysis of the obtained solid is reported in the table.

[Table] Ethylene Polymerization Examples 11-32 The catalyst components prepared in Examples 1-10 were mixed with Al-alkyl to prepare a catalyst, which was used in the polymerization of ethylene. Polymerization was carried out under the following conditions. 100 ml of anhydrous desulphurized and degassed n-heptane as cocatalyst, component (b) and finally the appropriate amount of component (a) in order
Added to autoclave and heated to desired temperature. Hydrogen and ethylene were added at predetermined partial pressures, and the total pressure during the polymerization was kept constant by continuously feeding ethylene. After a suitable reaction time, the polymerization was stopped, the suspension was removed from the autoclave, filtered and the polyethylene was dried in an oven to constant weight. The amounts of ingredients used, the conditions and temperature at which the polymerization was carried out, and the physical properties of the resulting polymers were recorded in the table. The catalytic index of the polymers was determined according to standard ASTM D1238 (conditions E and F) and is expressed in g/10 min.

【table】

[Table] Ethylene copolymerization examples 33 to 35 The catalyst components produced in Examples 1 to 10 are mixed with Al-alkyl to produce a catalyst, and the catalyst is mixed with ethylene to obtain a crystalline ethylene copolymer. and a small amount of alpha olefin. Copolymerization was carried out under the following conditions. Three autoclaves equipped with an anchor stirrer and heated to the desired temperature were fed in sequence with the following materials: 480 ml of anhydrous desulfurized and degassed n-
Heptane, 4 mmol of (iC ₄ H ₉ ) ₂ Al-O-Al(iC ₄ H ₉ ) ₂ as cocatalyst, appropriate amount of butene-
1. Desired amount of H ₂ and ethylene to a total pressure of 14 atmospheres. After 5 minutes, 10 mg of the solid catalyst component (a) as described in Example 1, suspended in 20 ml of n-heptane, are added under an overpressure of argon, and the total pressure is maintained with a continuous feed of ethylene. It was kept constant by doing this. The test was stopped after 10 minutes and the polymer was isolated after removing unreacted monomer. The amount of butene-1, polymerization conditions and physical characteristics of the resulting copolymers are reported in the table.

[Table] Example 36 A 1.5 autoclave with an anchor stirrer was fed in sequence at room temperature with the following substances:
0.7 g of [(iC ₄ H ₉ ) ₂ Al] ₂ O in n-heptane containing 134 g/
g of butene-1. It was heated to a temperature of 65° C. (butene-1 pressure = 7.5 atm) and hydrogen was added to a pressure of 9.5 atm, then ethylene was added to a pressure of 36 atm. 7.7 mg of the catalyst component obtained according to Example 1 in 20 c.c. of n-pentane were then added using a steel syringe under ethylene overpressure. Ethylene was added until a pressure of 39 atmospheres was reached (ethylene pressure = 29.5 atmospheres). During the test the pressure was kept constant by supplying ethylene.
The test was stopped after 2 hours, and the polymer was isolated after removing unreacted monomer and incubated in an oven for 70 minutes.
It was dried to constant weight at .degree. The amount of polymer was 220g. The yield is 120000g/g V
(28600g/g catalyst). The copolymer showed a butene content of 10.5% by weight by infrared spectroscopy.
The density is 0.9166 g/ ^cm3 , η-specific is 1.6 dl/g, MIE=1.75 g/10′, and MIF
= 180g/10′. Elastomeric copolymer of ethylene Example 37 22 mg of the catalyst component obtained according to Example 1 was
The catalyst for polymerization was prepared by mixing with 1 c.c. of Al(iC ₄ H ₉ ) ₃ in cc of n-heptane. 500 g of propylene at room temperature in a 3000
It was placed in an autoclave with a volume of cm ³ , the temperature was increased to 40° C. (propylene pressure = 16 atm) and ethylene was added to a pressure of 22 atm. The catalyst was then added via a steel syringe under an overpressure of argon. During the test, the pressure was kept constant by feeding ethylene. The test was stopped after 4 hours. The amount of polymer dried under vacuum was 150 g. The yield was 28000 g/g V (6800 g/g catalyst). The copolymer showed a propylene content of 39% by weight when subjected to infrared spectroscopy. X
Linear analysis showed that the copolymer had a polyethylene type crystallinity of 2% by weight. Example 38 500 g of propylene were added into the autoclave described in Example 37 at room temperature. temperature
The temperature was raised to 40°C (propylene pressure = 16 atm) and ethylene was added to 22 atm. Then 20
(iC ₄ H ₉ )-Al-O in 8 c.c. of n-heptane
2/mg of the catalyst component prepared according to Example ₃₇ mixed with a 0.5M solution of -Al( _iC4H9 ) was added via a steel syringe under an overpressure of argon. The pressure was kept constant by feeding ethylene during the test. Polymerization was stopped after 4 hours. The amount of polymer dried under vacuum was 160 g. The yield is
It was 31000 g/g V (7600 g/g catalyst).
When subjected to infrared spectroscopy, the copolymer showed a propylene content of 45% by weight. Upon X-ray analysis, the copolymer showed the presence of 3% by weight polyethylene type crystallinity. Polypropylene Polymerization Example 39 8 g of powdered anhydrous VCl ₃ was added to 100 g of anhydrous VCl 3 in the above container.
ml of _{anhydrous C2H5OH} . The resulting solution was evaporated until a solid product was obtained. 7.81 g of the solid product thus obtained was poured into 200 ml.
of SiCl ₄ and 8.8 mmol ethyl benzoate (EB) in heptane solution. 48 under reflux it
The solids formed were isolated by filtration, each washed with 50 c.c. of anhydrous n-heptane,
It was then dried under vacuum at 20°C for 1 hour. 4.77 g of the solid product thus obtained was
treated with a heptane solution containing ml TiCl ₄ and 2.2 mmol EB. Heat it to 120℃,
It was kept at that temperature for 2 hours. Go through that,
Then add the same amount of _TiCl4 again, let it react at the same temperature for 2 hours, pass through to remove _TiCl4 , and n- at 90° until the chlorine ions in the liquid disappear.
Washed with heptane. The solid, dried under vacuum, was analyzed and showed the following weight content: Ti = 4.4
%, V=24.2%, Cl=59.9%, EB=1.57%. Propylene polymerization was carried out under the following conditions: 3.75 mmol aluminum trialkyl mixture with the following gas composition (in % by volume) after hydrolysis: ethane = 9 isobutane = 49.4 n-butane = 41.2 propane = 0.16 isobutane = 0.24 was reacted at room temperature with 1.13 mmol of methyl paratoluate in 80 ml of n-heptane (anhydrous and desulfurized) for 5 minutes. 50 ml of the solution was contacted with 120 mg of the catalyst component prepared above. The remaining 30 ml was diluted to 1000 ml with n-heptane and added under nitrogen pressure into a 40°C temperature-controlled steel autoclave with a capacity of 3000 ml, equipped with an anchor stirrer and a thermometer. Propylene was flowed. In the same manner, the catalyst component suspension was then added therein. After closing the autoclave, add hydrogen.
It was then heated to 70°C while simultaneously feeding propylene to a total pressure of 7 atm. The pressure is kept constant during the polymerization by continuing to feed monomer. Polymerization was stopped after 4 hours and the polypropylene was isolated by treatment with methanol and acetone. The results of the polymerization are as follows: Yield = 2.33
Kg polymer/g catalyst, extraction residue with boiling n-heptane is 91.3%, η specific = 3.87.

[Brief explanation of drawings]

The drawing is a flowchart schematically showing a process for preparing a catalyst component for alpha-olefin polymerization according to the present invention and a mode of using the catalyst component for alpha-olein polymerization.

Claims (1)

[Claims] 1 General formula VCln(OR)m [In the formula, R is a hydrocarbon group having 1 to 18 carbon atoms, particularly an alkyl group having 1 to 10 carbon atoms, or a cyclocarbon group having 6 to 8 carbon atoms. Alkyl or allul or group R _1P Si
(OH) _3-P , where R ¹ is a hydrocarbon group,
and 1 _P 3, n is a number from 1.5 to 3, and m is 3-n], and the spectrum of ordinary VCl ₃ has d=5.75 Å, d=2.67 Å and d=
The maximum intensity diffraction line appearing at 1.74 Å is
At least 3 for the diffraction line at d = 5.75 Å
chlorine of trivalent vanadium with an X-ray powder spectrum that exhibits at least a 4-fold half-width broadening for the diffraction lines appearing at d = 2.67 Å and d = 1.74 Å, or such that the diffraction lines disappear. catalyst component for olefin polymerization, optionally containing a Ti halide and/or supported on MgCl ₂ . 2 n=2, m=1, and R is an alkyl group having 1 to 8 carbon atoms, Claim 1
Catalyst components as described in section. 3. A catalyst component according to claim 1 or 2, having the formula VCl ₂ (OC ₂ H ₅ ). 4 General formula VCln(OR)m [wherein R is a hydrocarbon group having 1 to 18 carbon atoms, particularly alkyl having 1 to 10 carbon atoms, cycloalkyl having 6 to 8 carbon atoms, or an allur or group R _1P Si
(OH) _3-P , where R ¹ is a hydrocarbon group,
and 1 _P 3, n is a number from 1.5 to 3, and m is 3-n], and in the spectrum of ordinary VCl ₃ , d = 5.75
Å, the maximum intensity diffraction lines appearing at d = 2.67 Å and d = 1.74 Å are at least three times as strong as those at d = 5.75 Å, and d = 2.67 Å
and a chlorinated compound of trivalent vanadium having an X-ray powder spectrum such that the diffraction line appearing at d = 1.74 Å has a half-width broadening of at least 4 times, or the diffraction line disappears. Contains halides and/or
A method for producing a catalyst component for olefin polymerization supported on MgCl ₂ , wherein the V compound is at least one selected from the group consisting of aliphatic, alicyclic and aromatic alcohols containing 1 to 18 carbon atoms. -OH
halogenated Si and Ti compounds, and then decomposed with a reagent selected from halogenated Si and Ti compounds capable of reacting with the -OH groups contained in the reaction product, where the halogenated Si compound is When used, it is optionally further reacted with a tetravalent Ti compound,
and optionally supported on MgCl ₂ in a conventional manner. 5 VCl ₃ is used as the V compound, C ₂ H ₅ OH is used as the -OH group-containing organic compound, and the decomposition is carried out using SiCl ₄ , claim 4.
The method described in section.