KR830000357B1 - Catalyst Component for Alpha-Olefin Polymerization - Google Patents

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Description

Catalyst Component for Alpha-Olefin Polymerization

The present invention relates to a catalyst component for alpha-olefin polymerization, and more particularly to a catalyst component for olefin polymerization, a catalyst prepared from the catalyst component, and a catalyst for stereospecifically polymerizing a mixture of alpha-olefin and ethylene Lt; / RTI >

U.S. Patent No. 3,642,746 discloses a catalyst which is useful for polymerizing olefins and which is a reaction product of a solid phase catalytic component charged with a MgCl ₂ / alcohol adduct and a halogenated Ti compound, such as TiCl ₄ , .

However, such catalysts have low catalytic activity and low stereoregularity and are therefore not suitable for stereoregular polymerization of alpha-olefins, especially propylene.

Aluminum alkyl partially compounded with an electron donor compound is contacted with a solid phase component prepared by reacting magnesium chloride in an appropriate device such as a bowl mill in the presence of an alcohol-electron donor compound and reacting the obtained product with TiCl ₄ to obtain a good catalyst A catalyst having activity and stereospecificity can be obtained. In preparing this catalyst, it is necessary to mechanically activate magnesium halide in the presence of an alcohol and an electron donor compound.

British Patent 1,485,234 in the name of the present applicant describes a catalyst for the polymerization of alpha-olefins prepared by reacting an Al alkyl compound partially compounded with a Lewis base with a solid component prepared from an adduct of magnesium halide and an alcohol .

In order to prepare highly active and stereoselective catalysts, it is necessary to pre-treat the adducts with a substance which can be reacted with an alcohol before reacting with the Ti halides.

Initiating the reaction with an additive of magnesium chloride, an alcohol, and a compound generally containing an active hydrogen atom, and pulverizing the magnesium chloride with an electron donating compound not containing an active hydrogen atom, and reacting the adduct with an alcohol It has been found that a catalyst component having good activity and stereospecificity in the polymerization of alpha-olefins can be prepared, without having to go through both of the pretreatment step and the substance capable of reacting and removing the alcohol from the adducts described above .

The catalytic component according to the present invention is a catalyst component in which Mg is a halide, a Ti compound and Mg are a complex of a halide and an electron donor compound, and a halogenated Ti compound containing at least one Ti-halogen bond and at least one of the following compounds Of the solid reaction product.

1) a mixture of an electron donor compound ED containing no active hydrogen atom and an adduct (a) of Mg with an electron donor compound AH containing an active hydrogen atom of a halogen atom and a monovalent isocyanate, wherein the hydrogen atom is Mg The electron donor compound ED is reacted in an amount of at least 0.05 moles per mole of the compound AH of the adduct.

2) the at least one Mg halide, the compound AH and the adduct (b) with the ED, wherein the compound ED is present in an amount of 0.05 to 1 mol per mol of the compound AH, and the adduct (b) This halide is prepared by conventional methods without co-milling.

After extraction with TiCl ₄ at 80 ° C for 2 hours, the amount of compound ED remaining in the solid product is between 0.3 and 3 moles per gram atom of Ti, and the amount of Ti compound that can be extracted with TiCl ₄ at 80 ° C is 50% or less.

The composition of the essential components of the adduct (a) is represented by the following structural formula.

MgX ₂ .nAH

n

6, 바람직하게는 1

n

4이고, AH는 특히 2~8개의 탄소원자를 함유하는 지방족 알코올, 오르토 위치가 치환되지 않는 페놀류와 같은 치환족 알코올, 예를들면 페놀, 4-t-부틸페놀, p-크레졸, 베타-나프톨 중에서 선택한 활성 수소원자를 함유하는 유기 화합물이다.In the formula, X is halogen, preferably Cl or Br, and 0.5

n

6, preferably 1

n

4, AH is in particular an aliphatic alcohol containing from 2 to 8 carbon atoms, a substituted aliphatic alcohol such as phenols in which the ortho position is not substituted, such as phenol, 4-t-butylphenol, p-cresol, Is an organic compound containing the selected active hydrogen atoms.

For example, adducts obtained from mixtures of lower aliphatic alcohols such as ethanol and 1-butanol with higher aliphatic alcohols such as 1-octanol or 2-ethyl-1-hexanol are particularly beneficial in the preparation of high activity catalysts .

Results similar to those achievable with alcohol may also be achieved as siltanols, primary amines, amides.

The adducts (a) and (b) can be prepared by reacting the compound AH and ED in the form of a combined metal compound, for example trivalent or tetravalent Ti compounds, in particular TiCl ₄ , Si and Al compounds such as alkyl silicates and Al alcohols Salts, CaCl ₂ , and CaI ₂ .

Adduct (a) is prepared in a different manner. A suitable method is to dissolve the Mg halide in an active hydrogen-containing compound followed by cooling the solution and adding an inert liquid that does not dissolve the adduct to precipitate the adduct. Other methods include reacting an RMgX compound (wherein R is an alkyl, cycloalkyl or aryl group having 1 to 20 carbon atoms and X is a halogen) with an alcohol ROH, wherein R is as defined above, and a hydrogen halide, according to a known method To produce an adduct MgX ₂ .nROH (where n is a number of 0.5 to 6).

The RMgX compound is dissolved in hydrocarbon (toluene, benzene) in the form of a complex with an ether such as dibutyl ether or dissolved in diethyl ether or used as a suspension in a non-polar solvent such as isooctane.

According to another method, the Mg metal, the alcohol ROH and the hydrogen halide react together to produce the adduct MgX 2 .nROH. The adduct may also be prepared by reacting a general formula ROMgX (X = halogen, R = alkyl, aryl or cycloalkyl group having 1 to 20 carbon atoms) and Mg alcoholate with hydrogen halide.

The ROMgX compound can be prepared by a known method; One of them is to react with a selected carbonyl compound from the aldehydes, ketones, ethers and halides of the carboxylic acid, especially to the greenery reagent.

Mg halides containing up to 1 mole of water per anhydrous or Mg gram atom can be used for the preparation of the adducts (a) and / or (b). For example, the adducts (a) and / or (b) can be prepared from halides by dehydration with halosilanes such as (CH ₃ ) ₂ SiCl.

The adduct (b) can also be prepared by a variety of different methods. A preferred method is to suspend the halide, AH and ED compounds in Mg in an inert hydrocarbon solvent (hexane, heptane, etc.) or a halogenated hydrocarbon solvent (CCl ₄ , CHCl _3, etc.).

Alternatively, the electron donating compound ED is reacted with the adduct (a) prepared in advance. Another method is to react a compound containing an active hydrogen atom, Mg, with an adduct prepared by previously reacting a halide with an electron-donor compound ED.

The reaction conditions are the conditions indicated in the preparation of the adduct (a). The adduct of the form (a) may be melted, the compound ED may be added thereto, and then cooled or an insoluble liquid may be added to separate the adduct (b).

In some cases, in particular, when it is desired to obtain a polymer having a controlled particle size, it is preferable to use adducts (a) and / or (b) of the spherical particle type having a controlled particle size distribution.

The reaction product between the small spherical Ti compound and the adduct provides a suitable catalyst for maintaining the morphology and morphology of the feed additive and for producing a spherical polymer having suitable mechanical resistance and flow properties.

Small spherical adducts can be prepared by a known method, for example, the method described in U.S. Patent No. 3,953,414.

The reaction between the Ti compound and the adduct (a) and the electron donor compound ED used as a component of the adduct (b) are compounds in which Mg can form an addition compound with a halide.

Particularly suitable compounds are alkyl, aryl and cycloalkyl esters of aromatic acids, in particular alkyl esters of benzoic acid and derivatives thereof.

Examples of suitable compounds include ethyl benzoate, p-butyl benzoate, methyl p-toluate and methyl p-methoxybenzoate.

Interesting results have shown that alkyl or alkyl-aryl ethers such as di-n-butyl ether and ethyl phenyl ether, ketones such as acetylacetone, benzophenone, and diamines such as N, N, N ', N'- tetramethylethylenediamine .

In some cases, in particular when the Ti compound is reacted with the adduct (a), the compound ED is preferably prepared by the original esterification reaction. For example, when the adducts (a) and / or (b) contain an alcohol or phenol, the reaction providing the catalyst component can be carried out in the presence of a halide of the aromatic carboxylic acid, for example benzoyl chloride have.

The treatment with benzoyl chloride can be carried out after the reaction between the Ti compound and the adduct (a).

The amount of the electron donor compound ED used in the mixture with the compound (a) or in the compound (b) is at least 0.5 to 3 mols, and is adhered to the catalyst component.

Generally, the compound ED reacts with (a) at a molar ratio of (a) to the compound AH of from 0.05: 1 to 5: 1.

The compound ED is also used as an adduct with an electron acceptor compound or a Lewis acid, unlike a halide. For example, it can be used as a halogenated Ti compound itself or as an adduct with a compound such as AlCl ₃ , BCl ₃ , CaCl ₂ , CaI ₂ , and the like.

The reaction with the Ti compound is preferably carried out by using an excess amount of the liquid Ti compound and separating the unreacted portion at the reaction boil.

It is effective to carry out the separation at a temperature at which the amount of the Ti compound soluble in TiCl ₄ at 80 캜 remaining in the catalyst component is 50% or less, preferably 20% or less, based on the total amount of the Ti compound.

As the Ti compound, it is preferable to use a hydrocarbon-soluble halogenated Ti compound, for example, TiCl ₄ , TiBr ₄ , TiI ₄ and a hydrocarbon-soluble halogen alcohol salt.

When TiCl ₄ is used as the Ti compound and the reaction is carried out in TiCl ₄ as the reaction medium, the reaction temperature is generally 50 ° C. to the boiling point of TiCl ₄ , preferably 100 ° C. to 135 ° C.

The separation of the excess TiCl ₄ not fixed on the carrier is preferably carried out at a temperature between 80 and 135 ° C. In order to promote the precipitation of the solid reaction product, it is suitable to add a hydrocarbon solvent.

The volume ratio between this solvent and TiCl ₄ is generally below 0.4.

The TiCl ₄ treatment is repeated several times, for example twice.

After reacting with TiCl ₄ , the solid is washed with a hydrocarbon solvent and then dried or suspended in a hydrocarbon solvent. This is a form in which the Ti compound and the electron donor compound ED are chemically bonded.

The Ti compound is not extracted by 50% or more at 80 캜 with TiCl ₄ , preferably not more than 20%, and the electron donor compound is present in the catalyst component after the treatment in an amount of 0.5 to 3 mol per Ti atom.

A catalyst component in order to solubilization to extract a fraction of the hydrocarbon insoluble Ti compound is (less than 20 ~ 30%) Ti compound when used as a composition containing the TiCl _3, such as a TiCl ₃ or product 2TiCl ₃ and AlCl ₃ in a hydrocarbon extender It is preferable to treat using dissolved compounds such as ICl3 or I2.

Therefore, the catalyst component contains 10 to 20% by weight (expressed as metal Mg) of a Ti compound of 0.5 to 10% by weight (expressed as metal Ti) as a main component, a Ti compound and a complex compound with an electron donor compound, Cargo and 0.5 to 3 moles of electron donating compound ED per Ti atom.

When the production reaction is started with an adduct with an alcohol, the alkoxy group is present in an amount of 0.5 to 5% by weight. In addition to the above main components, an organic or inorganic solid phase weight agent or carrier which does not react with Mg halides can be used.

Examples of the extender include polymers such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , B ₂ O ₃ , Na ₂ CO ₃ polyethylene, polypropylene, polystyrene, and polytetrafluoroethylene.

The catalyst for the synthesis of the alpha-olefin and the mixture thereof with ethylene according to the present invention is the following reaction product.

A) an Al alkyl compound wherein at least 5 to 90% is an adduct with an electron donor compound.

B) The above-described catalyst component.

An electron donor compound capable of forming a complex with an alkyl compound can be used to prepare the catalyst component (B).

The above-mentioned components are prepared before contacting with the catalyst component (A), or the Al alkyl compound and the electron donor compound are contacted separately with the catalyst component (B).

The catalytic component (B) is first contacted with the electron donor compound in advance and then contacted with the Al alkylated compound or vice versa. A preferred method is to contact the Al alkyl compound in advance with the electron donating compound before reacting with the catalytic moiety (B).

The amount of the electron donor compound used for preparing the catalyst component (A) is 5 to 90%, preferably 25 to 50%, of the Al alkyl, generally 0.1 to 0.9 mole per mole of Al alkyl, 0.2 To 0.4 mol.

Particularly suitable electron donor compounds are esters of aromatic acids. Examples of the ester include alkylbenzoates having alkyl, alkoxyl, hydroxyl substituents and halogen atoms in the benzene ring and derivatives thereof.

Examples of such compounds include ethyl p-aminobenzoate, methyl p-toluate, ethyl p-hydroxybenzoate ethyl 3,4-dihydroxybenzoate and ethyl 3,6-dichloro-4- There is a number.

Examples of other useful esters include esters of aliphatic carboxylic acids having 1 to 10 carbon atoms, such as ethyl acetate, acetonate, or inorganic acid esters such as ethyl carbonate and ethyl silicate, alkyl phosphates or zinc salts. Examples of useful electron donor compounds also include ether, ketone, aldehyde, aliphatic and aromatic carboxylic acids, quinones, anhydrides and halides of aliphatic and aromatic carboxylic acids, secondary and higher amines, amides, lactones, phenols, alcohols, organic isocyanates, Alkyl, aryl- or cytaralkyl-imide, and the like.

Examples of the compounds belonging to the above-mentioned class include the following compounds. Butyl ether, diphenyl ether, tetrahydrofuran, ethyl-methyl ether, benzoic acid, salicylic acid, phthalic acid, acetic acid, oxalic acid, maleic acid, Benzaldehyde, benzaldehyde, benzenesulfonamide, benzenesulfonamide, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, maleic anhydride, , o-methyl-phenol, 2,5-di-t-butylphenol, p-methoxyphenol, p-hydroxy-phenol, t-butyl alcohol, ethylene glycol, diglycol-monobutyl ether

Al alkyl compounds suitable for the preparation of component (A) are Al trialkyl compounds or Al alkyl compounds containing two or more Al atoms in different ones through oxygen or nitrogen atoms.

, Al-(C₁₂H₂₅)₃, (C₂H₅)₂Al-O-Al(C₂H₅)₂,

Examples of the compound include Al (C ₂ H ₅ ) ₃ , Al (iC ₄ H ₉ ) ₃ , Al (nC ₄ H ₉ ) ₃ ,

, Al- (C ₁₂ H ₂₅ ) ₃ , (C ₂ H ₅ ) ₂ Al-O-Al (C ₂ H ₅ ) ₂ ,

The same results as described above can be obtained in an Al phenoxyl compound or an Al dialkyl monohydride analogous to that described in Italian Patent Application No. 25217A / 75.

Compounds containing at least two Al atoms bridged to the Al trialkyl and the Santo or Nitrogen atoms can be prepared by reacting an Al dialkyl halide or Al alkyl with a system that provides a halide such as a halide + . ≪ / RTI >

The alkyl halides are generally present in the mixture in a molar ratio of 50%.

The Al alkyl compound is used such that the Al / Ti ratio is generally between 10 and 1,000 and preferably between 20 and 500.

The catalyst of the present invention is particularly suitable for the production of crystalline polymers and copolymers of propylene.

In addition to propylene, butene-1 and 4-methyl-pentene-1 can be polymerized. They can also be used to polymerize ethylene.

The propylene crystalline polymer can be prepared by various conventional methods. One of these methods is to pre-polymerize propylene until at least 70 to 80% by weight of the total polymer is obtained, and then add the ethylene-propylene mixture or the ethylene-propylene mixture when the amount of polymerized ethylene contained in the final polymer is 5 to 30% Ethylene is polymerized in one or more steps.

A propylene-ethylene mixture containing a relatively low percentage of ethylene and having a polymerized ethylene content of 5% by weight or less can be polymerized.

When the catalyst component (A) is an Al alkyl compound which does not form a complex with the electron donor, the catalyst is particularly suitable for the production of amorphous copolymers of ethylene and alpha olefins.

The new catalyst can be used in conventional polymerization conditions, that is, the polymerization reaction is carried out in a liquid phase or in the presence or absence of an inert hydrocarbon solvent, or in a vapor phase.

If the polymerization temperature is 40 to 70 ° C, the polymerization pressure is atmospheric pressure or higher.

The following examples are described for the purpose of explaining the present invention and are not intended to limit the present invention.

[Example 1]

A) Manufacture of elemental ingredients

Methylbenzoate was added dropwise to 25 g of anhydrous MgCl ₂ (H ₂ O content <0.5%; crystal form α, crystal diameter = 380 A °) suspended in 300 cc of n-heptane at room temperature under stirring. After 1 hour, 39.2 g of n-butyl alcohol was added dropwise thereto. The temperature was set at 80 DEG C and the reaction was continued for 1 hour. At the end of the reaction, the solvent was distilled off under reduced pressure at a temperature of 50 캜 to obtain 70 g of solid matter.

25 g of the thus obtained product was stirred and treated with TiCl ₄ 210CC at 100 ° C for 2 hours. 51CC of heptane was added dropwise to the suspension while stirring. Stirring was stopped after 15 minutes, and the solid matter was tilted. Removing the liquid material between the ponbeop, washed in 80 ℃ 4 times the solids with heptane each time 130CC, followed by washing at room temperature for the remaining time until the TiCl ₄ is destroyed.

The product was partially dried at 50 &lt; 0 &gt; C under vacuum and partially held in suspension to be used for the polymerization test.

The dried solid exhibited the following weight composition. : Ti = 3,9%, Mg = 16.55%, ethyl benzoate = 8.6% (1), BuOJ = 2.2% (1).

(1) Chromatographic analysis.

B) Polymerization of propylene in solvent

Hexane 870CC previously saturated with nitrogen was introduced into a 2.5-liter stainless steel high-pressure pot equipped with a magnetic stirrer and kept in a weak propylene flow. Separately, the following materials were introduced into the tailed flask in sequence. Heptane 130CC, Al triisobutyl 1g and methyl p-toluate 0.253g, and after 5 minutes, the catalyst composite thus obtained was introduced into a high-pressure pot at 45 ° C in a stream of propylene. The high pressure cooker was covered, and H ₂ 275CC was introduced.

The pressure was then pressurized to 7 eq and the temperature was raised to 60 &lt; 0 &gt; C. The polymerization was carried out at normal pressure and at room temperature for 4 hours. At the polymerization boom, the resulting polymerization slurry was centrifuged at room temperature. After centrifugation, a polymer in powder form was obtained, which was then dried in an oven at 70 DEG C in the presence of nitrogen.

The atactic polymer was centrifuged and the solution was evaporated to dryness. Analysis of this polymer (powdered polymer + atactic polymer) gave the following data on the catalyst residues and the yield can be calculated from this data.

Ti = 4.5 ppm, Mg = 22 ppm, Cl = 95 ppm.

The total isotactic index calculated by the following equation was 94%.

IIt =

II powder is an index for a polymer that has been dried by centrifugation and is determined by extraction with boiling heptane for 3 hours. The characteristics of the powdery polymer are as follows. Density = 0.36 g / cm ³ , melt flow index = 3.8 g / 10 min, flexural strength = 14,800 kg / cm ² .

[Examples 2 to 5]

A different form of alcohol than that used in Example 1 was used. The results obtained are shown in Table 1.

[Examples 6 to 11]

In Example 1, the operation mode of MgCl ₂ / n-butyl alcohol / ethyl benzoate adduct was changed. The results are shown in Table 2.

[Examples 12 to 18]

In Example 1, the ratio of MgCl ₂ / alcohol / ethyl benzoate was changed. The results are shown in Table 3.

Table 1

EB = ethyl benzoate; MFI = melt flow index; AD = density or bulk density.

Table 2

EB = ethyl benzoate; MFI = melt flow index; AD = apparent density or bulk density; r · t = room temperature

Table 3

EB = ethyl benzoate; MFI = melt flow index; AD = apparent density or bulk density.

[Example 19]

In this test, the ethyl benzoate in Example 1 Method 1 by the described except the addition of: using a MgCl ₂ and 2 molar ratio of BuOH to prepare the adduct. Benzoate was added in an amount of 0.2 in terms of the benzoate / alcohol molar ratio during the TiCl ₄ treatment, and then the procedure described in Example 1 was carried out.

The results obtained were as follows.

Ti = 3.25%; Mg = 17.10%; Cl = 61.80%; EB = 6.9%; BuOH = 2.1%

Polymerization test

The composition of the catalyst residue in the polymer is as follows.

Ti = 5.5 ppm, Mg = 20 ppm, Cl = 86 ppm.

Total isotactic index (IIt) 92.0 Isotactic index measured on powder (II powder) = 94.5%

The melt flow index of the powder = 3.3 g / 10 min

Density = 0.45 g / cm &lt; ³ &gt;

Flexural strength = 13250 kg / cm ₂

[Example 20]

4.5 g of MgCl2 (47.5 mmol) was suspended in 73 ml of n-heptane containing 1.1 ml (7.3 mmol) of ethyl benzoate at 25 DEG C and reacted for 2 hours. The heptane was removed in vacuo at 50 &lt; 0 &gt; C. A white solid that is generated in the processing 110 ℃ for 2 hours TiCl ₄ 150ml, and then the TiCl ₄ was filtered off, followed by adding an equal volume of TiCl _4. After reacting it at 110 DEG C for 2 hours, it was washed with n-heptane at 90 DEG C until the chloride ion in the filtrate disappeared. After drying in vacuo, the catalyst components had the following composition as a result of the analysis.

Ti = 2.2%, Cl = 61.97%, EB = 7.2%

This compound was used as a catalyst component for propylene polymerization test conducted under the following conditions. (Volume%) after hydrolysis, that is,

Ethane = 9, isobutane = 49.4, n-butane = 41.2, propane = 0.16, isobutene = 0.24

Of Al trialkyl is reacted with 1.25 mmol of ethyl p-toluate in 80 ml of n-heptane (anhydrous and desulfurized) at room temperature for 5 minutes.

50 ml of this solution was brought into contact with 100 mg of the catalyst component and the remaining 30 ml was diluted to 1,000 ml with n-heptane and introduced into a 3000 ml capacity steel autoclave equipped with a magnetic anchor stirrer and a thermostat while maintaining the temperature at 40 ° C in the presence of nitrogen And propylene was introduced thereinto.

In the same manner, a suspension of the catalyst component is subsequently introduced. After the autoclave was closed, hydrogen was added to a partial pressure of 0.1 atm, and at the same time, propylene was heated to 60 deg. C while feeding until the total pressure reached 5 atm. During the polymerization by feeding the monomer, the pressure was maintained at the pressure.

After 4 hours, the polymerization was stopped and treated with methanol and acetone to separate the polypropylene. 375 g of propylene corresponding to a quantity of 170,000 g of polymer per tig was obtained. The yield of the heptane residue was 92%.

[Example 21]

Treatment was carried out as in Example 20, but 95 mmol of 4-tert-butylphenol was used instead of phenol. TiCl ₄ , and dried under vacuum to obtain the following composition (% by weight).

Weight ratio: Ti = 2.49, Mg = 20.07 Ethyl benzoate = 9

The polymerization test was repeated as in Example 20 to obtain the following results.

Polymer g / Tig = 230,000, heptane residual amount = 92.5%,? ₁ = 1.54 dl / g

[Example 22]

Treatment was carried out as in Example 20 but 95 mmol of p-cresol was used instead of phenol. The polymerization test conducted under the conditions of Example 20 gave the following results.

Polymer g / Tig = 230,000, heptane residual amount = 92%,? ₁ = 1.85 dl / g

[Example 23]

Treatment was carried out as in Example 20 but using 95 mmol of beta-phenol instead of phenol. The polymerization test conducted under the conditions of Example 20 gave the following results.

Polymer g / Tig = 230,000, heptane residual amount = 91.5%,? ₁ = 2.00 dl / g

[Example 24]

Small spherical (particle size <50μ) MgCl ₂ obtained from molten MgCl ₂ , 4n-C ₄ H ₉ OH, 17.41 g (51 mmol) of 3.3 nC ₄ H ₉ OH by spray-cooling using a NIRO atomizer, It was suspended in 200ml of n- heptane and, at the same time, the benzoyl chloride was added dropwise 2.9ml (25.6 mmol) of TiCl ₄ in 100ml 0 ℃. After 30 minutes, 200 ml of TiCl ₄ was added to the dropping funnel, and the temperature was gradually raised to 110 ° C. This was reacted for one hour, was then separated by filtration and the solid component, and was treated with TiCl ₄ 200ml. After reacting for 2 hours at 110 ℃, until the TiCl ₄ was filtered off, and the disappearance of the chlorine ions of the solids the filtrate was washed with n- heptane at 90 ℃. As a result of analysis, the catalyst composition showed the following composition (%).

Mg = 27.26, Ti = 2.01, Cl = 55.5, EB = 8

The propylene polymerization test conducted under the conditions of Example 20 yielded a polymer having a yield of 208,000 g of polymer per Tig, with a residual heptane content of 93% and? ₁ = 2.12 dl / g.

80% of the polymer particles had a particle size of 105-710 mu. No particles having a particle size of 105 mu m or less were found.

[Example 25]

A solution of 1.5 mol of C ₂ H ₅ OH in anhydrous HCl at a HCl / Mg ratio of 3.3 was added at 5 ° C with stirring to a solution of 3.1 mol of C2H5MgCl in dibutyl ether.

The mixture was stirred at room temperature for 1.5 hours and then the solid product was separated by filtration, washed with n-heptane and vacuum dried at 35 &lt; 0 &gt; C.

20 g of this solid product is added to 500 cc of n-heptane in which ethylbenzoate is dissolved in a ratio of 0.2 mol per gram atom of Mg. The suspension was heated at 60 DEG C for 1 hour.

200 cc of the suspension was reacted with TiCl ₄ at 110 캜 for 2 hours so that the ratio of Ti / Mg became 15.1. The suspension was heat filtered and then repeatedly washed with n-heptane until no TiCl ₄ was detected and then dried.

Analysis of the solids revealed the following composition:

(weight%)

Ti = 2.7, Cl = 63, Mg = 19, ethylbenzoate = 7.6

0.075 g of the product was used in the polymerization test under the same conditions as in Example 1 except that only the pressure was maintained at 9 atm. 465 g of a polymer having a residual heptane content of 92% (yield = 230 mg of polymer per g of Ti) was obtained.

[Example 26]

The procedure of Example 25 was repeated except that a 0.85 molar solution of n-C4H9MgCl of dibutyl ether was used.

The composition (% by weight) of the solid product after the reaction with TiCl ₄ is as follows.

Ti = 2.92, Mg = 20, Cl = 62.9, ethyl benzoate = 6.7

0.057 g of the solid product was used in the propylene polymerization test under the same conditions as in Example 25. [ 385 g of a polymer having a heptane residual amount of 93.5% (yield = 203 kg of polymer per 1 g of Ti) was obtained.

[Example 27]

9.72 g of a metal slice of 30-50 mesh was reacted at 40 ° C for 1 hour, and then reacted with a toluene solution of C ₂ H ₅ OH containing HCl having a HCl / Mg ratio of 2.77 at 60 ° C for 1 hour.

20 g of the solid product are added to 500 cc of n-heptane in which ethylbenzoate is dissolved in a ratio of 0.2 mol per gram of Mg atom. The suspension was heated at 60 &lt; 0 &gt; C for 1 hour.

200 cc of the suspension was reacted with TiCl ₄ having a Ti / Mg ratio of 20 at 120 ° C for 2 hours.

The solid is heated until the suspension is filtered not TiCl ₄ is detected and washed with n- heptane.

The solid 0.043 was used in the compaction test under the same conditions as in Example 25.

270 cc of a polymer having a residual heptane content of 90% was obtained.

[Example 28]

30 g of MgCl ₂ .6H ₂ O was refluxed with 100 cc of (CH ₃ ) ₃ SiCl for 100 hours. The solid product was filtered off, washed with n-heptane and dried at 60 ° C. The water content was 0.71% by weight.

9.1 g of the product was suspended in 100 cc of n-heptane, and then 0.194 mol of C 2 H 5 OH and 0.016 mol of benzoate dissolved in 25 cc of n-heptane were added dropwise. The mixture was reacted at room temperature for 1 hour, mixed with 350 cc of TiCl ₄ , and reacted at 100 ° C for 2 hours. The suspension was heated to dryness, washed with n-heptane until no TiCl ₄ was detected, and then dried.

The composition was as follows.

Ti = 3.5%, Mg = 17.3%, Cl = 58%, ethylbenzoate = 9%

Under the same conditions as in Example 20, 0.037 g of a solid product was used in the propylene polymerization test.

190 g of a polymer having a residual heptane content of 91.1% (yield = 153 kg of polymer per 1 g of Ti) was obtained.

[Example 29]

(CH ₃ ) ₃ SiCl ₂ was used instead of the compound of Example 28.

The results of the propylene polymerization test were as follows.

Yield = 164 kg of polymer per Tig, residual amount of heptane = 91%

Claims (1)

A halogenated Ti compound having at least one Ti-halogen bond and (A) an electron donating compound ED containing no active hydrogen selected from alkyl, cycloalkyl, and aryl esters of aromatic acids, and one kind of an electron donating compound ED containing an active hydrogen atom selected from aliphatic and alicyclic alcohols and phenols which are not ortho-substituted phenols Wherein the above-mentioned compound AH is a compound in which magnesium is present in an amount of 0.5 to 6 moles per mole of the halide, and the electron donating compound ED is an electron donating compound Present in an amount of 0.05-1 moles per mole of compound AH in the adduct. (B) an addition product of magnesium halide with the above-mentioned electron donor compound AH and electron donor compound ED (b), wherein the electron donor compound AH is added in an amount of 0.5 to 6 moles of magnesium per mole of halide after the extracted present and for electron donor compound ED is an electron donor compound AH per mole is present in an amount from 0.05 to 1 mole.] min and a solid product by reaction of one and two hours at 80 ℃ as the product of TiCl ₄ in and the amount of the ED compound, which remains in the solid phase of water equal to the molar amount of 0.3 to 3 per gram atom Ti, alpha 80 ℃ or less amount 0.1-5% of Ti compound to be extracted with TiCl ₄ in a-olefins, and increase of a mixture of alpha olefin and ethylene hapyong Catalyst component.