KR800000971B1 - Components of catalysts useful for polymerization of -olefins - Google Patents

Abstract

Catalyst components for the polymn. of C3 and higher lolefins are prepd. by treating Ti halides(TiCl4) with Mg dihalides(MgCl26EtOH) or their complexes which have been decompd. with 0.5 moles electron donor or ammonia/mol Mg dihalide. THe decompd. Mg halide product has an X-ray pattern consisting of a halo rather than sharp lines with intensity max.

Description

Catalyst Component for Polymerization of Alpha-Olefins

The present invention provides novel catalyst components for stereoregular polymerization of alpha-olefins containing three or more carbon atoms, mixtures of alpha-olefins with other olefins and / or ethylene, processes for their preparation, catalysts obtained therefrom and It relates to the use of the above catalyst for the production of crystalline polymers and copolymers of alpha-olefins.

Alpha prepared by reacting a halogen containing a titanium compound with a reaction product of a silicon compound or a metal compound of a metal belonging to Groups I to III of the Periodic Table of the Elements and an electron donor compound containing magnesium halides and active hydrogen atoms Catalyst components suitable for the polymerization of -olefins are known (French Republic Nos. 2,200,291 and 2,26,339).

When a catalyst obtained from such a catalyst component is used for olefin polymerization containing three or more carbon atoms, a polymer containing a significant amount of atactic polymer is obtained.

French Republic patents 2,282,909 and 2,300,772 describe catalytic components useful for the polymerization of alpha-olefins actually produced by the aforementioned French Republic patents, with the difference being that of the silicone compounds or groups I to III of the periodic table. The reaction between the metal belonging to, in particular the addition product of aluminum compound and magnesium halide, takes place in the presence of an electron donor compound. The catalysts produced from such catalyst components have sufficient steric properties, but are extremely poor in activity and must pass through a process of purifying the polymer from the catalyst residues at the end of the polymerization. When the polymerization reaction is carried out in the presence of hydrogen as the molecular weight modifier and when the Al-alkyl group partially complexed with the electron donor is used as the cocatalyst, the activity is rather extremely low.

According to the techniques described both in French Patent Nos. 2,283,909 and 2,300,772, addition products of magnesium halides using an electron donor containing active hydrogen react with magnesium halides in which the electron donor is suspended in an inert hydrocarbon solvent. It is prepared by making.

This adduct is then reacted with the Si compound or Al compound in the presence of an electron donor that does not contain active hydrogen. The product thus obtained is then treated with liquid hydrogen containing a Ti compound. The reaction product between the Mg halide addition product and the Si compound or Al compound comprises or consists essentially of Mg dihalide. In X-ray analysis, it shows a spectrum representing the typical maximum intensity diffraction line of the Mg dihalide, or the maximum intensity diffraction line has a light ring with the maximum intensity shifted relative to the line itself by decreasing the intensity. To form.

Starting from a product containing Mg dihalide obtained by decomposing an adduct of Mg dihalide using a compound composed of at least one electron donor, having satisfactory properties for both steric characteristics and activity, In order to obtain a solid catalyst component useful for the polymerization of alpha-olefins containing three or more carbon atoms, such degradation products must exhibit an X-ray powder spectrum, where the maximum intensity is not seen in the Mg-halogen powder spectrum and instead A light ring with intensity moved about that line appears.

Furthermore, the solid catalyst component containing the Ti compound consisting of a product obtained by reacting the decomposition product with a halogenated Ti compound soluble in hydrocarbons is soluble in TiCl ₄ at 80 ° C. by 50% by weight, preferably in excess of 20% by weight. It should not contain Ti compounds.

The solid catalyst component of the present invention is composed of a halide of Mg in combination with an halogenide, a Ti compound, and an electron donor containing no active hydrogen atoms, and the molar ratio of Mg / Ti in the catalyst component is 5 to 100, and the electron donor The number of moles of g is 0.4 to 3.5, preferably 1 to 2 with respect to Ti 1g atom. The catalyst component is obtained by reacting the following materials. In other words,

a) at least one halogenated Ti compound soluble in hydrocarbons

b) a product consisting of Mg halides obtained by decomposing the adduct between at least one Mg halide and the organic electron donor present in the following adduct and / or ammonia in an amount of at least 0.5 mole per mole of said Mg halide ( The decomposition reaction is carried out with a compound other than a Ti compound that is reactive with the electron donor of the adduct, the decomposition product having its maximum intensity in its X-ray powder spectrum instead of the maximum intensity line which appears in the Mg halide. Moved wheels), and

c) an electron donor free of active hydrogen which can be reacted with a) or with b) before a) and b) react.

In the case of decomposition products of adducts of MgCl ₂ , the X-ray powder spectrum shows that the maximum intensity of the light ring is comprised between 2.44 and 2.97 kPa, and 2.56 kPa for the rhombohedral MgCl ₂ . In the case of hexagonal MgCl ₂ , the line appearing at 2.75 Å is actually disappeared. In the case of decomposition products of adducts from MgCl ₂ , the light rings appear instead of the line at 2.93 kV.

Suitable organic electron donors for the preparation of adducts with Mg dihalide consist of both active hydrogen atom containing compounds and active hydrogen atom free compounds.

Particularly interesting solid catalyst components are aliphatic or aromatic alcohols, phenols, amines, or halogens containing Si or Sn compounds such as SiCl ₄ and SnCl ₄ , or metal compounds of Al such as Al-trialkyls; These are obtained from the decomposition products of MgCl ₂ adducts using ammonia.

The catalyst component is a compound Cl which is 4 weights when an aromatic acid, in particular a tetravalent Ti compound which is insoluble in TiCl ₄ at 80 ° C. with 0.4 + 3.5 g mol / Tig atoms such as, for example, ethyl benzoate and 80 ° C. It is contained so that it may become an amount of% or less.

This solid catalyst component is prepared in several ways. An example of the preferred method among these starts with Mg dihalide prepared by dissolving Mg dihalide in an electron donor and continuously precipitating the adduct by cooling the solution or adding an inert liquid which does not dissolve the adduct. . The resulting adduct exhibits a homogeneous chemical composition as a whole and, through chemical decomposition, provides a product based on Mg dihalide which exhibits a spectrum with certain properties during X-ray analysis.

Starting Mg dihalide adducts with electron donors containing active hydrogens may also contain electron donors without active hydrogen atoms.

The amount of such compounds is generally 0.5 mole per mole of Mg halogen. Examples of such compounds are organic acid alkyl esters, especially alkyl esters of aromatic acids and aliphatic or aromatic ethers.

This adduct also contains, for example, a chemically harmonized form of a tetravalent Ti compound, in particular a metal compound, such as a halogen-containing compound such as alkyl silicate, alcoholic acid Al. In fact, the catalyst of the invention also starting from adducts of Mg compounds, Ti halides and alcohols prepared by dissolving Mg halides in alcohols and adding tetravalent Ti halides to the solution according to Belgian patent No. 840,058 It is possible to obtain the ingredients.

This adduct may also be prepared by grinding a mixture of Mg halides with a predetermined amount of organic electron donor containing active hydrogen atoms for 20 to 60 hours, such as in a vibratory mill containing steel balls. have.

According to this technique, it is possible to obtain a catalyst having a high activity of an organic electron donor containing an active hydrogen atom per mole of Mg dihalide even if the number of moles of the adduct is relatively small.

This adduct can also be produced in the form of ultra-spherical spheres by spray cooling or spray drying according to known techniques. Using the catalyst obtained in this case, a polymer having a narrow particle size distribution can be obtained.

Examples of active donors containing active hydrogens useful in the preparation of this adduct include aliphatic or aromatic alcohols and thioalcohols, phenols, primary and secondary amines, ammonia, amides and aliphatic or aromatic carboxylic acids.

Specific examples of such compounds include methyl, ethyl, n-butyl, hexyl alcohols, phenols, cresols and ammonia.

Generally the amount of active hydrogen containing compound is in the range of 0.5 to 6 moles per mole of Mg halide. In the case of adducts with alcohols, the best results are achieved when the molar number is 2-6. This adduct also contains up to 2 moles of water molecules, usually per mole of Mg dihalide, in chemically bound form as well.

Decomposition of adducts into or consisting of dihalide is actually done with materials that are reactive with active hydrogen atoms different from Ti compounds. Such materials include, in particular, halides of metal organic compounds, Si, Sn and Sb compounds Al and B belonging to groups I to III of the periodic table.

Representative examples of such materials include, for example, halogen containing compounds of Si, Sn, halides of SbCl ₃ , halides of Si-alkyls, halides of Sn-alkyls and hydrogen halides of Sn, with preferred compounds being SnCl ₄ and SiCl ₄ and other suitable materials include halides of Si-tetraalkyls and Si-alkyls.

Examples of Al metal organic compounds that can be used include Al-alkyls such as Al (i-Bu) ₃ and AlEt ₃ , AlR ₂ Cl, AlRCl ₂ , Al ₂ Et ₃ Cl ₃ , AlEt ₂ Br, Al (OEt) Cl and Halides of the same Al-alkyls, also Al (OEt) Et ₂ , Al (i-Bu) ₂ H and other compounds.

Preferred compounds include, for example, Al-triisoalkyls such as Al-triisobutyl.

More useful metal organic compounds include Mg, Ca or Zn compounds such as Grignard reagent, Mg-monoalkoxides, Mg-dialkyl or Mg-diphenyl compounds, Zn-monoalkyl or Zn-dialkyl compounds. .

Generally, the amount of reactive material is at least 1 mole per g atom of active hydrogen present in the adduct.

The decomposition reaction is sometimes carried out in the liquid phase in the presence of an inert solvent. When the reactant is volatile, it can also be used in the gas phase.

The active hydrogen atom-free electron donor useful for preparing Mg dihalide and adducts may be used with any material capable of forming adducts with Mg dihalide. Representative examples thereof are the following compounds.

Alkyl-, aryl-, cycloalkyl-esters of organic and inorganic acids,

Ethers such as di-n-butyl ether and diethyl ether and cyclic ethers such as tetrahydrofuran and dioxane.

Ketones such as acetone, benzophenone and cyclohexanone.

Anhydrides of carboxylic acids.

-Aldehydes such as benzaldehyde, anisealdehyde.

Nitriles such as acetonitrile and benzonitrile.

-Trisubstituted phosphines.

-Azo compounds.

Chlorides of aliphatic acids.

-Dialkyl substituted amides.

-Alkylamides.

Tertiary amines and their oxides;

-Substituted lactams.

Organic isocyanates.

-POCl ₃ , PSCl ₃

Adducts with electron donors that do not contain active hydrogen atoms usually contain up to 6 moles of the electron donor.

The decomposition of the adduct is carried out using a material that is reactive and capable of removing at least some electron donors from the adduct.

Examples of the decomposable substance include organic compounds of Al, Zn, Mg, and B metals, particularly the following compounds.

AlR ₃ ㆍ AlR _3-n Xn, MgR ₂ , MgRX (Greenir).

ZnBX, ZnR ₂ , BR _3-n Xn.

Wherein each R 120 is an alkyl, cycloalkyl, aryl group containing 120 C atoms, and n is an integer of less than 3, X is halogen, OR and H.

Decomposition conditions are the same as the conditions indicated for the adduct with the active hydrogen atom-containing electron donor.

Not all electron donors can be removed from the adduct. In this case, the electron donor remaining in the decomposition product can be used as the reactant material C) for reaction with the halogenated Ti compound.

The Ti compound used to prepare the catalyst component according to the present invention is a halogen containing compound of tetravalent Ti such as, for example, TiCl ₄ , TiBr ₄ and Ti halogen-alcoholate.

The reaction with the Ti compound is preferably carried out in an excess of Ti liquid compound, and then the unreacted compound is separated at a temperature where the amount of the Ti compound extractable with TiCl ₄ at 80 ° C. in the reaction product is 50% by weight or less.

If TiCl ₄ is used as the reagent and reaction zone, the reaction temperature will generally be a temperature between 50 ° and TiCl ₄ boiling points, in particular 90 ° and 135 ° C. When operating under reduced pressure, a higher temperature may be used. The separation of excess TiCl ₄ (filtration, precipitation, etc.) is preferably carried out at a high temperature of 80 ° C. or higher, in particular in the range of 90 ° to 135 ° C.

Particularly suitable catalyst components for the preparation of catalysts with high activity and steric properties are prepared starting from adducts of MgCl ₂ with alcohols in the following manner. That is, the MgCl ₂ adduct reacts simultaneously or sequentially with Si or Sn or Sb compounds and electron donors, which reactions are carried out at temperatures ranging from room temperature to the boiling point of the mixture, and sometimes in the presence of an inert solvent such as n-heptane. Under an inert gas atmosphere.

The resulting solid product was filtered, washed with n-heptane and dried in vacuo, and finally reacted with TiCl ₄ at a temperature between 100 ° and 150 ° C., preferably 130 ° C., with unreacted TiCl ₄ at least 80 ° C. When removed at high temperature, the stock is washed with n-heptane and dried in vacuo.

When the adduct decomposition is carried out with an aluminum metal organic compound, in particular Al-trialkyl, the active hydrogen-free electron donor undergoes an appropriate reaction such as to destroy this electron donor after the decomposition reaction to cause the electron donor and Al— The possibility of reaction between alkyls should be eliminated.

Decomposition products obtained from adducts of dihalides with active hydrogen free or containing electron donors may be combined with active hydrogen free electrodonors prior to or during the reaction with the halogenated Ti compounds. Electron donors are generally used in amounts of at least 0.1 moles and no more than 0.5 moles per mole of Mg dihalide in the monolysis product.

The catalyst solid component containing the tetravalent Ti compound can be treated with a substance capable of reducing the Ti valency to 4 or less before mixing with the Al metal organic compound to form a polymerization catalyst.

For example, the present catalyst component can be reacted with an Al-alkyl compound, in which the reduced product thus obtained is used to form the polymerization catalyst.

The electron donor C) may be any compound capable of forming an adduct with Ti halide. These may be the same as those used for the preparation of adducts with Mg dihalide. Examples of suitable compounds are alkyl, cycloalkyl or aryl esters of organic acids, especially esters of aromatic acids such as benzoic acids. Examples of such esters are ethyl benzoate, p-methoxy ethyl benzoate, methyl p-toluate, and p-butoxy benzoate. Examples of other useful compounds are ethers such as di-n-butyl and di-phenylether or ketones such as benzophenone, diamines such as N, N, N ', N'-tetramethylethylenediamine.

The alpha-olefin polymerization catalyst according to the present invention consists of a product obtained by mixing the following components.

A) Al metal organic compound containing no hydrogen atom directly bonded to Al.

B) an organic electron donor in an amount such that compound A) is combined with B) in an amount of 10% to 95%.

C) Ti-containing solid catalyst component as described above.

In the present polymerization catalyst, the molar ratio of Al / Ti is 10 or more, in particular 20 to 500. Compounds A) and B) are preferably mixed before contacting them with component C). Components A), B and C) may be added simultaneously, or component A) may be added to component C) before reacting with B). However, this is not a preferred case.

The electron donor used as component C) is obtained by the reaction of an Al-trialkyl with, for example, an active hydrogen atom-containing electron donor, such as to form a complex compound and / or a substitution reaction product represented by the following scheme, Al metal organic Any compound that can react with the compound (component A) may be used.

Examples of electron donors which can be used as component B) include amines, amides, ethers, thioethers, ketones, nitriles, phosphines, stybins, arsines, phosphoramides, aldehydes, esters and thioesters. And alcohol salts, organic acids, and amides and salts of the group to the group metals of the periodic table. In the case of salts, they can be prepared by the reaction between component A) and the organic acid.

Preferred compounds are esters of organic and inorganic acids. Examples of particularly suitable are esters of aromatic acids such as benzoic acid, p-methoxybenzoic acid, alkyl esters of p-toluic acid. Examples of such esters are ethyl benzoate, p-methoxy ethyl benzoate, methyl p-toluyl acid and ethyl, and p-butoxy benzoate.

Other examples of useful esters are diethyl carbonate, ethyl pivalate, ethyl acetate, dimethyl maleate, alkyl silicate or aryl, in particular ethyl silicate Si (OC ₂ H ₅ ) ₄ .

Al metal organic compounds usable as component A) are for example Al-triethyl, Al-triisobutyl, Al-tripropyl,

Al-trialkyl compounds such as are preferred.

It is also possible to use Al metal organic compounds containing two or more Al atoms which are bonded to each other via an O atom or an N atom.

가 있다.Examples of such compounds include (C ₂ H ₅ ) ₂ -Al-O-Al- (C ₂ H ₅ ) ₂ ,

There is.

Al metal organic compounds described in Belgian patent number 842,866 are also useful compounds.

Other useful compounds are Al-dialkylhydrates, Al-dialkylalkoxides and Al-alkyltrialkoxides such as triethoxy Al-ethyl and tributoxy Al-butyl.

The metal organic compound A) can also be used in mixtures with Al-alkyl monohalogen compounds used in amounts of up to 1 mole per mole of compound A).

The active hydrogen free electron donor present in component C) may be the same as used as component B) or may be other than an active hydrogen free compound. Also in this case, the compound which can form a complex compound with Mg dihalide can be used for component C) manufacture. As already mentioned above, esters are preferred compounds.

The present catalysts according to the invention are preferably used for the polymerization of alpha-olefins or mixtures thereof containing 3 or more carbon atoms and / or ethylene. They are especially suitable for the preparation of crystalline polymers or copolymers of propylene.

The polymerization reaction is carried out according to a known method by operating in the liquid phase or in the gas phase in the presence or absence of an inert hydrocarbon diluent such as hexane, heptane, cyclohexane. The polymerization temperature is usually in the range of 0 ° to 150 ° C., preferably 40 ° to 90 ° C., and is carried out under atmospheric pressure or higher. When producing crystalline copolymers of propylene, it is advantageous to polymerize propylene until 60 to 90% of the homogeneous polymer of the entire polymer composition is obtained, in which the polymerized ethylene component is 5 to 30 to the composition. One or more stages of polymerization of the ethylene-propylene mixture or ethylene alone are followed to occupy the weight percent.

It is also possible to polymerize propylene and ethylene mixtures in order to obtain copolymers containing up to 5% by weight of ethylene.

The following examples are intended to illustrate the present invention and are not intended to limit it.

Example 1

21.8 g of MgCl ₂ ㆍ 6C ₂ H ₅ OH (58.7 mmol) prepared by dissolving 1 mol of chloride in 6 mol of ethanol at 70 캜 and cooling to 20 캜 was crystallized from 2.34 ml of ethyl benzoate in 200 ml of SiCl ₄ in an inert gas atmosphere. It was made to react with the solution containing (15.6 mmol) at 60 degreeC for 18 hours. After filtration, washing with 250 mL of anhydrous n-heptane and drying in vacuo, the resulting white solid was treated with 100 mL of TiCl ₄ at 130 ° C. for 2 hours. Thereafter, TiCl ₄ was filtered off at 130 ° C., the same amount was added again, and then reacted at the same temperature for 2 hours, filtered at 130 ° C. to remove TiCl ₄ , and washed with n-heptane at 90 ° C. As a result of analysis until no more chlorine ions were detected in the filtrate, the vacuum-dried solid had a titanium content of 1.43 wt%, magnesium content of 18.70 wt%, chlorine content of 65.2 wt%, and benzoic acid content of 8-9 wt%.

Propylene polymerization tests performed using catalyst components such as these compounds are shown in Table IV.

EXAMPLES 2, 3, and 4

The elemental analysis value according to the molar ratio change between MgCl ₂ and ethyl benzoate of the catalyst component prepared according to the method of Example 1 is shown in Table I.

Propylene polymerization tests conducted using such compounds as catalyst components are shown in Table IV.

[Examples 5 and 6]

The elemental analysis value according to the variation of the number of ethyl alcohol molecules covalently bonded with MgCl _{2 in} the starting adduct of the catalyst component prepared according to the method of Example 1 is shown in Table 2.

Propylene polymerization tests conducted using such compounds as catalyst components are shown in Table IV.

EXAMPLES 7 AND 8

The elemental analysis of the type of alcohol covalently bonded with MgCl _{2 in} the starting adduct of the catalyst component prepared according to the method of Example 1 is shown in Table III.

Propylene polymerization tests conducted using such compounds as catalyst components are shown in Table IV.

TABLE I

TABLE II

TABLE III

Example 9

12.8 g of MgCl ₂ · 6C ₂ H ₅ OH (34.5 mmol) prepared according to the method of Example 1 was reacted with 95 ml of pure SiCl ₄ in a nitrogen atmosphere. The reaction mixture was heated until boiling to react for 16 hours.

Then 0.86 mL (5.75 mmol) of ethyl benzoate was added and the whole was boiled for 2 hours. As a result, a white solid was filtered off, washed several times with n-heptane and dried under vacuum, followed by drying with vacuum in 150 mL of TiCl ₄ at 2O < 0 > C. Treated for hours. Next, TiCl ₄ was removed by hot filtration and the same amount of fresh TiCl ₄ was added again to repeat the treatment for 2 hours. The composition of the white solid obtained by removing TiCl ₄ and washing with n-heptane at 90 ° C. until no more chlorine ions in the filtrate was detected and dried in vacuo was as follows.

Titanium = 2.39 wt%

Magnesium = 20.53 wt%

Chlorine = 62.20 wt%

Ethyl benzoate = 8% by weight + 9% by weight

The propylene polymerization tests carried out using these compounds as catalyst components are shown in Table IV.

Example 10

Anhydrous MgCl ₂ 21.5 was dissolved in 200 ml of anhydrous ethanol, 5.65 ml of ethyl benzoate was added thereto, and the solution was reacted at 70 ° C. for 1 hour. Evaporation under vacuum separated the white crystalline solid represented by the following general formula.

11.30 g (30.5 mmol) of the compound described above was reacted with 84 mL of pure SiCl ₄ in a nitrogen atmosphere. The mixture was heated until boiling and left at the same temperature for 18 hours.

The resulting white solid was filtered off, washed several times with n-heptane and dried under vacuum, then treated with 150 ml of TiCl ₄ at 130 ° C. for 2 hours.

The TiCl ₄ was then removed by hot filtration and the same treatment was repeated for 2 hours by adding the same amount of fresh TiCl ₄ . After removing TiCl ₄ , washing was continued with n-heptane at 90 ° C. until no more chlorine ions in the filtrate were detected and dried under vacuum to obtain a solid composition as follows.

Titanium = 2.32 Weight%

Magnesium = 20.53 weight%

Chlorine = 63.12 weight%

Propylene polymerization tests conducted using these compounds as catalyst components are shown in Table IV.

Example 11

MgCl ₂ · 3.8 C ₂ H ₅ OH (20 mmol) was reacted for 16 hours while heating under reflux with 120 mL of SiCl ₄ in a nitrogen atmosphere. As a result, the white solid was filtered off, washed several times with n-heptane, dried under vacuum, and treated with 130 ml of an aqueous solution of 0.5 ml (3.3 mmol) of ethyl benzoate and 150 ml of TiCl ₄ . I was. The solid was liberated by filtration, washed with n-heptane and dried under vacuum. As a result of the analysis, Ti content 2.73 wt% Mg content 21.1 wt% and chlorine content 63.9 wt% were shown.

The propylene polymerization tests carried out using these compounds as catalyst components are shown in Table IV.

Example 12

7.3 g of MgCl ₂ .6C ₂ H ₅ OH was treated with SiCl ₄ in the vapor entrained by nitrogen streams, using SiCl ₄ which combined 400 ml. 2.2 g of the solid product thus obtained was suspended in a solution containing 30 ml of n-heptane, and 0.30 ml of ethyl benzoate was added under stirring to react at room temperature for 3 hours.

The liquid was removed and dried, then the free white solid was treated with 100 mL of TiCl ₄ at 130 ° C. for 2 hours. TiCl ₄ was removed by filtration and the same treatment was repeated by adding the same amount of fresh TiCl ₄ . After removing TiCl ₄ , the solid was obtained by washing with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ions in the filtrate were detected.

Ti = 3.96 weight%

Mg = 19.90 weight%

Cl = 59.08 Weight%

Example 13

15.7 g of MgCl ₂ .6C ₂ H ₅ OH prepared according to the method of Example 1 was introduced into a glass flask boiled with a solution consisting of 200 ml of n-heptane, 177 ml of SiCl ₄ and 1 ml of ethyl benzoate, followed by boiling. The reaction was carried out for a time.

As a result, the composition of the product liberated by filtering the white solid, washing three times at 60 ° C. with 100 ml of n-heptane, drying under vacuum and treating twice with TiCl ₄ according to the manner described in Example 1 was as follows.

Titanium = 39 weight%

Magnesium = 18.95 weight%

Chlorine = 64.80 weight%

Propylene polymerization tests conducted using these compounds as catalyst components are shown in Table IV.

Example 14

7.3 g (16.5 mmol) of MgTiCl ₄ (OC ₂ H ₅ ) ₂ .4C ₂ H ₅ OH prepared according to the method described in Belgian Patent No. 840,058 with 50 ml of SiCl ₄ and 0.83 ml (5.5 mmol) of benzoic acid in an inert gas. The mixture was reacted at 60 ° C. for 92 hours.

The resulting solid was filtered off, washed with 200 mL of anhydrous n-heptane, dried under vacuum and treated with 100 mL of TiCl ₄ at 130 ° C. for 2 hours. At the end of this treatment, TiCl ₂ was removed by filtration and again, an equal amount of fresh TiCl ₄ was added and reacted at the same temperature for 2 hours. Then, TiCl ₄ was removed by filtration and chlorine in the filtrate was n-heptane at 90 ° C. The solid obtained by washing and drying in vacuo until no more ions were detected showed analytical results of 1.30 weight% titanium, 21.20 weight% magnesium and 62.90 weight% chlorine.

Table IV shows the results of a propylene polymerization test using this compound as a catalyst component.

Example 15

6 g (63 mmol) of anhydrous MgCl ₂ were suspended in 100 mL of anhydrous n-heptane containing 1.16 mL of TiCl ₄ in a nitrogen atmosphere. ₅ ml of C ₂ H ₅ OH was added to the suspension and reacted at 20 ° C. for 3 hours while stirring. The solid was separated by a large-cantation method, washed with 25 ml of n-heptane, dried under vacuum, and then treated at 60 ° C. for 16 hours with a solution of 100 ml of SiCl ₄ and 1.5 ml (10 mmol) of ethyl benzoate. The resulting solid was filtered off, washed with anhydrous-heptane 250, dried under vacuum and treated with 100 ml of TiCl ₄ at 130 ° C. for 2 hours. At the end of this treatment, TiCl ₄ was removed by filtration, and the same amount of new TiCl ₄ was added again and reacted at the same temperature for 2 hours, and then TiCl ₄ was filtered off, until no more chlorine ions in the filtrate were detected. The solid washed with n-heptane at < RTI ID = 0.0 > C < / RTI > and dried under vacuum showed an analysis of 1.47 wt% titanium content, 21.87 wt% magnesium content and 60.04 wt% chlorine content.

The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 16

6.4 g (24.6 mmol) of MgCl ₂ · 6C ₂ H ₅ OH were reacted with a solution of 70 mL of SnCl ₄ and 0.615 mL (4.1 mmol) of ethyl benzoate for 2 hours in an inert gas atmosphere.

As a result, the white solid was filtered, washed with 250 ml of anhydrous n-heptane, dried under vacuum, and treated with 100 ml of TiCl ₄ at 130 ° C. for 2 hours. The TiCl ₄ was then removed by hot filtration, the same amount of fresh TiCl ₄ was added and reacted at the same temperature for 2 hours, then the TiCl ₄ was removed by filtration, at 90 ° C. until no more chlorine ions in the filtrate were detected. The solid obtained by washing with n-heptane and drying in vacuo was found to be 4.1% by weight titanium, 19.05% magnesium content and 58.93% chlorine content.

The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 17

5.3 g (19 mmol) of MgCl ₂ · 3.8C ₂ H ₅ OH was reacted with a mixture of 100 ml of antimony contaminated and 0.49 ml (3.3 mmol) of ethyl benzoate for 20 hours at 70 ° C. in an inert gas atmosphere.

As a result of the reaction, the white solid was filtered off, washed with 250 ml of anhydrous n-heptane, dried under vacuum, treated with 100 ml of TiCl ₄ at 130 ° C., and after 2 hours, TiCl ₄ was removed by filtration and the same amount of new TiCl ₄ was added. After reacting for 2 hours at a temperature, the TiCl ₄ was filtered off, washed with n-heptane at 90 ° C. and dried under vacuum until no more chlorine ions were detected in the filtrate. A magnesium content of 20.47% by weight and a chlorine content of 63.10% by weight.

The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 18

5.6 g (21.4 mmol) of MgCl ₂ · 3.8C ₂ H ₅ OH was stirred in 250 ml of a mol heptane solution of aluminum triisobutyl, added batchwise, and heated to 80 ° C. for 4 hours after 1 hour. After filtration, washing with 200 ml of anhydrous n-heptane, and freed solid were suspended in a solution of 0.54 ml (3.6 mmol) of ethyl benzoate and 50 ml of n-heptane and the dilute suspension was left for 2 hours under stirring at room temperature.

Results were collected by filtration and the product The white solid obtained was dried under vacuum at 130 ℃ hayeoseo with TiCl ₄ 100㎖ after treatment for 2 hours was filtered off and the TiCl ₄ and cheopga an equal volume of fresh TiCl ₄ again to react for 2 hours, and then the TiCl ₄ The solid obtained by rinsing with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ion in the filtrate was detected was analyzed, and the resultant analysis showed that the titanium content was 2.05 wt%, magnesium content 21.25 wt%, chlorine content 59.3 wt%, and The benzoic acid content was found to be 59.3 weight%.

The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 19

31 g (15.7 mmol) of MgCl ₂ · 6NH ₂ were stirred at room temperature and added to 270 ml of a mol heptane solution of aluminum triisobutyl and heated to 80 ° C. for 4 hours after 1 hour. The precipitate obtained by filtration was washed with 200 mL of anhydrous n-heptane and the free solid was suspended in a solution of 0.39 mL (2.6 mmol) of ethyl benzoate and 50 mL of n-heptane, and the suspension was left under stirring at room temperature for 2 hours. .

This insoluble product was filtered off and dried in vacuo. As a result, the white solid was treated with 100 ml of TiCl ₄ at 130 ° C. for 2 hours, and then TiCl ₄ was filtered off and added with the same amount of fresh TiCl ₄ for 2 hours at the same temperature, followed by filtration of TiCl ₄ , and chlorine in the filtrate. Washed with n-heptane at 90 ° C. until no more ions were detected. The solid obtained by drying in vacuo was found to have a titanium content of 2.08 wt%, magnesium content of 23.05 wt% and chlorine content of 61.54 wt%.

Table IV shows the results of the propylene polymerization test using these compounds as catalyst components.

Example 20

2.93 g (11 mmol) of MgCl ₂ 3.8C ₂ H ₅ OH was reacted with a solution of 10.5 mL (83 mmol) of Al (C ₂ H ₅ ) ₂ Cl and 60 mL of n-heptane in a nitrogen atmosphere for 1 hour. Heated to 80 ° C. for 3 hours. The precipitate obtained was filtered off and washed with 200 ml of n-heptane.

The free solid was suspended in a solution of 0.27 mL (1.8 mmol) ethyl benzoate and 50 mL n-heptane and the suspension was stirred at room temperature for 2 hours. Insoluble product was filtered off and dried in vacuo. As a result, the white solid was treated with 100 ml of TiCl ₄ at 130 ° C. for 2 hours, and then TiCl ₄ was filtered off and the same amount of new TiCl ₄ was added and reacted at the same temperature for 2 hours, followed by filtration of TiCl ₄ , The solid obtained by washing with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ions were detected was found to be 1.07 wt% titanium content, 22.9 wt% magnesium content and 62.86 wt% chlorine content.

The results of the propylene polymerization test using this compound as a catalyst component are shown in Table IV.

Example 21

_4.5 g (18.3 mmol) of MgCl ₂ .2.5H ₂ O.2.3C ₂ H ₅ OH were added batchwise to 200 mL of a mol-heptane solution of Al (iso-C ₄ H ₉ ) ₃ under stirring at room temperature, followed by 80 after 1 hour. Heated to < RTI ID = 0.0 > C < / RTI > for 4 h and then filtered and washed with 200 ml of dry n-heptane. The free solid was suspended in a solution of 0.46 mL (3.05 mmol) ethyl benzoate and 50 mL n-heptane and the suspension was stirred at room temperature for 2 hours. After filtered off the product and vacuum drying was treated for 2 hours at 130 ℃ the obtained white solid was filtered off with TiCl ₄ 100㎖ the TiCl ₄ and by the addition of an equal volume of fresh TiCl ₄ were reacted at the same temperature for 2 hours and then TiCl ₄ , solids obtained by washing with n-heptane at 90 ° C. and drying in vacuo until no more chlorine ions in the filtrate were detected were found to have a titanium content of 2.06% by weight, a magnesium content of 16.39% by weight and a chlorine content of 60.4. It appeared in weight percent. The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 22

A steel cylindrical vibratory grinder having a height of 80 mm and a diameter of 125 mm was filled with 10 ml of steel bowl 150, 92 g (0.97 moles) of anhydrous MgCl ₂ and 56.5 ml (0.97 moles) of anhydrous ethyl alcohol, followed by grinding for 40 hours at 30 ° C. MgCl ₂ · C ₂ H ₅ OH complex was prepared. 8.5 g of the complex thus obtained was treated with a solution of 1.5 ml of ethyl benzoate and 50 ml of SiCl ₄ at 60 ° C. for 40 hours.

The product was filtered off, washed with n-heptane and dried in vacuo and treated with 150 ml TiCl ₄ at 130 ° C. for 2 hours under stirring. After filtered off the TiCl ₄ were repeatedly treated with the same volume of fresh TiCl _4. The composition of the solid obtained by washing the filtered product with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ions in the filtrate were detected was as follows.

Ti = 1.12 wt%

Mg = 20.82 wt%

Cl = 63.3 wt%

The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 23

19.6 g (82 mmol) of MgCl ₂ ㆍ (C ₄ H ₈ ) ₂ O was added batchwise to 328 mL of a mol heptane solution of aluminum triisobutyl under stirring at room temperature, and heated to 80 ° C. after 1 hour at 6 ° C. It was kept for an hour and then filtered off and washed with 300 mL of anhydrous n-heptane. The free solid was suspended in 137 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirred at room temperature for 2 hours.

The product was filtered off and dried in vacuo. The white solid was treated with 200 ml of TiCl ₄ at 130 ° C. for 2 hours, then the TiCl ₄ was filtered off and the same amount of fresh TiCl ₄ was added and reacted at the same temperature for 2 hours. ₄ , the solid obtained by washing with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ions in the filtrate was detected was found to be 1.54% titanium content, 21.35% magnesium content and 67.9% chlorine content. It was found to be weight percent. The results of the propylene polymerization test using these compounds as catalyst components are shown in Table IV.

Example 24

17.7 g (97 mmol) of MgCl ₂ CH ₃ COOC ₂ H ₅ was added in a batchwise batch to 290 ml of a mol heptane solution of aluminum triisobutyl under stirring at room temperature, and heated to 80 ° C. after 1 hour to maintain the copper temperature for 6 hours. Maintained. The product was filtered and washed with anhydrous n-heptane and the free solid was suspended in 162 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirred at room temperature for 2 hours.

The product was collected by filtration was dried under vacuum and over again, the addition of an equal volume of fresh TiCl ₄ by eliminating the TiCl ₄ and then the resulting white solid for 2 hours at 130 ℃ to 200㎖ TiCl _4, the reaction at the same temperature for 2 hours and then The solid obtained by filtration of TiCl ₄ , washing with n-heptane at 90 ° C. and drying in vacuo until no chlorine ion in the filtrate was detected any more was found to have a titanium content of 1.45% by weight, 20.05% by weight of magnesium and chlorine content. It was found to be 65.7% by weight. The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 25

15.3 g (100 mmol) of MgCl ₂ CH ₃ COCH ₃ was added in batches to 250 ml of a mol heptane solution of aluminum triethyl under stirring at room temperature, heated to 80 ° C. after 1 hour, and then maintained at the same temperature for 6 hours. . The product was filtered off and washed with 300 mL of anhydrous n-heptane and the free solid was suspended in 170 mL of heptane solution containing 0.1 mol of ethyl benzoate and stirred at room temperature for 2 hours.

The product was collected by filtration, dried in vacuo and the resulting white solid was treated for 2 hours at 130 ℃ with TiCl ₄ 200㎖ the TiCl ₄ was filtered off and added to an equal volume of TiCl ₄ again reacted at the same temperature for 2 hours and then TiCl ₄ , solids obtained by washing with n-heptane at 90 ° C. and drying in vacuo until no more chlorine ions were detected in the filtrate were analyzed and analyzed to be 2.22% by weight titanium, 18.98% magnesium and 62.47% chlorine. It was found to be weight percent.

The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 26

13.6 g (100 mmol) of MgCl ₂ CH ₃ CN was added to a batch of 250 ml of a mol heptane solution of aluminum triisobutyl under stirring at room temperature, and heated to 80 ° C. after 1 hour to maintain the same temperature for 2 hours. The product was filtered off and washed with 300 mL of dry n-heptane. The free solid was suspended in 170 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirred at room temperature for 2 hours.

The product was separated by filtration and dried in vacuo, and the result after the resulting white solid for 2 hours at 130 ℃ with TiCl ₄ 200㎖ by the addition of distilled off over an equal volume of TiCl ₄ to TiCl ₄ reaction at the same temperature for 2 hours and then TiCl ₄ , the solid obtained by washing with n-heptane at 90 ° C. and drying in vacuo until no more chlorine ions in the filtrate were detected was found to have a titanium content of 2.17% by weight, 18.58% by weight of magnesium and 61.75% by chlorine. It was found to be weight percent.

The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 27

10.6 g (42 mmol) of MgCl ₂ 2C ₅ H ₅ N was added to a small batch of 200 ml of a mol heptane solution of aluminum triisobutyl under stirring at room temperature, and heated to 80 ° C. for 1 hour, and maintained at the same temperature for 2 hours. Then, it was filtered and washed with 300 ml of dry n-heptane. The free solid was suspended in 70 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirring continued for 2 hours at room temperature. 0.1 product was filtered off and dried in vacuo. The resulting white solid was treated with 200 mL of TiCl ₄ at 130 ° C. for 2 hours. Thereafter, TiCl ₄ was filtered off and the same amount was added again. It was reacted for 2 hours at the same temperature, and then filtered to remove TiCl ₄ and washed with n-heptane at 90 ° C. until no more chlorine ions were detected in the filtrate.

The vacuum dried solid product had a content of 1.21 wt% titanium, 21.27 wt% magnesium and 68.03% chlorine.

The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 28

49 mmol of MgBr ₂ ㆍ (C ₂ H ₅ ) ₂ O were added in batchwise batches to 110 ml of a mol heptane solution of aluminum triisobutyl under stirring at room temperature, and heated to 80 ° C. after 1 hour to maintain the same temperature for 2 hours. Filtration was washed with anhydrous n-heptane 300 ml. The free solid was suspended in 80 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirring continued for 2 hours at room temperature.

The product was collected by filtration and dried in vacuo, and the result after the resulting white solid for 2 hours at 130 ℃ with TiCl ₄ 200㎖ filtered off by the TiCl ₄ and TiCl ₄ cheopga the same amount of reaction at the same temperature for 2 hours and then TiCl ₄ , the solid obtained by washing with n-heptane at 90 ° C. and drying in vacuo until no more chlorine ions in the filtrate was detected was analyzed and found to be 0.72 wt% titanium and 15.93 wt% magnesium. .

The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 29

44 mmol of MgCl ₂ · 2γ-butyro-lactone were added to a batch of 250 ml of a mol heptane solution of aluminum triisobutyl under stirring at room temperature, and heated to 80 ° C. after 1 hour to maintain the copper temperature for 2 hours, and then And washed with 300 ml of anhydrous n-heptane. The free solid was suspended in 73 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirring continued at room temperature for 2 hours.

The product was separated by filtration and dried under vacuum, and that the result after the resulting white solid for 2 hours at 130 ℃ with TiCl ₄ 200㎖ filtered off by the addition of TiCl _4, and again the same amount of the TiCl ₄ reaction at the same temperature for 2 hours and then The solid obtained by filtration of TiCl ₄ , washing with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ions in the filtrate were detected was found to be 1.62 wt% titanium, 19.02 wt% magnesium and chlorine content. It was found to be 61.12% by weight.

The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 30

MgCl ₂ ㆍ 2CH ₃ CON (CH ₃ ) was added 8.3 g (30.4 mmol) in small batches to 150 ml of a mol heptane solution of aluminum triisobutyl with stirring at room temperature, followed by heating to 80 ° C. after 1 hour. It was kept for an hour and then filtered off and washed with 300 mL of anhydrous n-heptane. The free solid was suspended in 51 ml of a heptane solution containing 0.1 mol of ethyl benzoate and stirring continued for 2 hours at room temperature.

The product was separated by filtration and dried under vacuum, and that the result after the resulting white solid for 2 hours at 130 ℃ with TiCl ₄ 200㎖ filtered off by the addition of TiCl _4, and again the same amount of the TiCl ₄ reaction at the same temperature for 2 hours and then The solid obtained by filtration of TiCl ₄ , washing with n-heptane at 90 ° C. and drying under vacuum until no more chlorine ions in the filtrate were detected was found to have a titanium content of 3.95 wt%, a magnesium content of 13.29 wt% and a chlorine content. It was found to be 57.16% by weight.

The results of the propylene polymerization test using this product as a catalyst component are shown in Table IV.

Example 31

41.6 g of fine spherical MgCl ₂ · 3C ₂ H ₅ OH was obtained from the molten MgCl ₂ · 6C ₂ H ₅ OH by spray cooling (by nitro atomizer) and heat flux removal of alcohol under vacuum at 50 ° C.

This adduct was treated with aluminum triisobutyl followed by TiCl ₄ as described in Example 18. Analysis of the solid catalyst component obtained by this method showed a titanium content of 1.98% by weight, a magnesium content of 18.60% by weight, and a chlorine content of 62% by weight.

Under the condition A, a propylene polymerization test was carried out using 39 mg of the catalyst component. The polypropylene obtained had an intrinsic viscosity 2.03 TiCl ₄ heptane residue 92% and the following particle size distribution.

710 500 microns = 21.1%

500 250 microns = 60.3%

250 125 microns = 16.2%

[Comparative Example]

15.7g을 50℃에서 3시간 진공증발시켰다.Of ethyl benzoate prepared as described in Example 10

15.7 g was evaporated at 50 ° C. for 3 hours.

The product thus obtained was treated with 150 ml of TiCl ₄ at 130 ° C. for 2 hours. The TiCl ₄ was then removed by hot filtration and the same amount of fresh TiCl ₄ was added to repeat the treatment for another 2 hours. When TiCl ₄ was removed, the product was washed with n-heptane at 90 ° C. until no more chlorine ions were detected in the filtrate. The vacuum-dried solid was analyzed to be 8.2% by weight titanium and 3.8% by weight ethyl benzoate.

Propylene polymerization tests conducted using these compounds as catalyst components are reported in Table IV.

Propylene Polymerization in Solvents

Condition A.

After hydrolysis, 5 mmol of an aluminum trialkyl mixture having the following composition of gas (% by weight) was reacted with 1.25 mmol of methyl para-toluate in 80 ml of n-hexane anhydrous and desulfurized product at room temperature for 5 minutes.

Ethane = 9

Isobutane = 49.4

n-butane = 41.2

Propane = 0.16

Isobutene = 0.24

50 ml of the solution thus obtained was contacted with an appropriate amount of catalyst component prepared according to each of the examples described above. The remaining 30 mL was diluted to 1000 mL with -hexane and introduced into a 3000 mL forced autoclave equipped with an anchor-type magnetic stirrer and a thermometer temperature-controlled at 40 ° C under nitrogen pressure, followed by propylene Was introduced. Next, the catalyst component suspension was introduced in the same manner. The autoclave was sealed and heated to 60 ° C. while adding hydrogen to bring the partial pressure to 0.1 atm and simultaneously supplying propylene to a total of 5 atm. Such pressure was kept constant throughout the prepolymerization reaction by continuing the monomer feed.

After 4 hours, the polymerization was stopped and treated with methanol and acetone to isolate polypropylene. The results of the polymerization tests conducted using the catalyst components described in each of the examples described above under the conditions described above are reported in Table IV.

Condition B.

1.25 mmol of aluminum trialkyl described in Condition A was reacted with 0.37 mmol of methyl para-toluate in 80 ml of n-hexane (anhydrous desulfurized product) at room temperature for 5 minutes.

50 mL of this solution was contacted with an appropriate amount of catalyst component prepared according to each of the examples described above. The remaining 30 ml was diluted to 500 ml using n-heptane and introduced into a 1000 ml forced autoclave equipped with an anchor-type magnetic stirrer and a thermometer temperature controlled at 40 ° C. under nitrogen pressure, and propylene was introduced therein. I was.

Subsequently, the catalyst component suspension was introduced and treated in the same manner as described in Condition A.

Condition C

1.25 mmol of aluminum triisobutyl was reacted with 0.25 mmol of methyl para-toluate in 80 ml of n-hexane (anhydrous desulfurized product) at room temperature for 5 minutes. 50 mL of this solution was contacted with an appropriate amount of catalyst component prepared according to each of the examples described above. The remaining 30 ml was diluted to 500 ml using n-hexane, introduced into a capacity 1 autoclave equipped with an anchor-type magnetic stirrer and a thermometer temperature adjusted to 40 ° C. under nitrogen pressure, to which propylene was introduced. . Subsequently, the catalyst component suspension was introduced and operated in accordance with the method described in Condition A.

Condition D.

2.5 mmol of aluminum triethyl was reacted with 0.64 mmol of para-toluic acid in 80 ml of n-hexane (anhydrous desulfurized product) at room temperature for 5 minutes. 50 ml of the solution was contacted with an appropriate amount of catalyst component prepared according to each of the examples described above. The remaining 30 ml was diluted to 500 ml with n-hexane and introduced into a capacity 1 autoclave equipped with an anchor-type magnetic stirrer and a thermometer temperature adjusted to 40 ° C. under nitrogen pressure, to which propylene was introduced.

The catalyst component suspension was introduced and operated in accordance with the method described in Condition A.

Condition E.

2.5 mmol of aluminum triethyl was reacted with 0.64 mmol of para-toluic acid in 80 ml of n-hexane (anhydrous desulfurized product) at room temperature for 5 minutes. 50 ml of the solution was contacted with an appropriate amount of catalyst component prepared according to each of the examples described above. The remaining 30 ml was diluted to 500 ml with n-hexane and introduced into a capacity forced autoclave equipped with an anchor-type magnetic stirrer and a thermometer adjusted to 40 ° C. under nitrogen pressure, to which propylene was introduced.

The catalyst component suspension was introduced and operated in accordance with the method described in condition A.

Condition F.

1.25 mmol of the aluminum alkyl mixture described in Condition A was reacted with 0.37 mmol of methyl para-toluate in n-hexane (anhydrous desulfurized product) for 5 minutes at room temperature.

50 ml of this solution was contacted with the appropriate amount of catalyst component prepared in each of the examples described above. The remaining 30 mL was diluted to 500 mL with n-hexane, introduced into a 1 L forced autoclave equipped with an anchor magnetic stirrer and a thermometer temperature controlled at 40 ° C. under nitrogen pressure, to which propylene was introduced.

In the same manner, the catalyst component suspension was introduced. After closing the autoclave, hydrogen was added to the partial pressure to 0.2 atm, and then heated to 60 ° C. with propylene being supplied simultaneously to a voltage of 9 atm. This pressure was kept constant during the prepolymerization reaction while the monomer feed was continued.

After 4 hours the polymerization was stopped and the polypropylene was treated with methanol and acetone. The results of polymerization tests conducted using the catalyst components described in each example under the above-described conditions are reported in Table IV.

Condition G.

1.25 mmol of aluminum triisobutyl was reacted with 0.25 mmol of para-toluic acid in 80 ml of n-hexane (anhydrous desulfurized product) at room temperature for 5 minutes. 50 ml of this solution were contacted with the appropriate amount of catalyst component prepared according to each of the examples described above. The remaining 30 ml was diluted to 500 ml with n-hexane, introduced into a 1000 ml capacity autoclave equipped with an anchor-type magnetic stirrer and a thermometer temperature adjusted to 40 ° C. under nitrogen pressure, and propylene was introduced thereto.

In the same way a catalyst component suspension was introduced here. After the autoclave was sealed, hydrogen was added to a partial pressure of 0.1 atm, and then heated to 50 ° C. with propylene being supplied simultaneously to a voltage of 5 atm. This pressure was kept constant throughout the prepolymerization reaction by continuing the supply of the monomer.

After 4 hours the polymerization was stopped and the polypropylene was isolated by treatment with methanol and acetone. The results of the polymerization tests performed using the catalyst components described in each example under the above-described conditions are shown in Table IV.

Condition H

1.25 mmol of aluminum triisobutyl was reacted with 0.25 ml of methyl para-toluate in 80 ml of n-hexane (anhydrous desulfurized product) at room temperature for 5 hours. 50 ml of this solution was reacted with the appropriate amount of catalyst component prepared in each of the examples described above. The remaining 30 ml was diluted to 500 ml with n-hexane, and put into a 1,000 ml forced autoclave equipped with an anchor-type magnetic stirrer and a thermometer temperature-controlled at 40 ° C. under nitrogen pressure, and propylene was introduced thereto.

In the same way, a catalyst component suspension was introduced. After the autoclave was sealed, hydrogen was added to a partial pressure of 0.1 atm, and then heated to 70 ° C. while simultaneously supplying propylene to a voltage of 5 atm. This pressure was kept constant throughout the prepolymerization reaction by continuing the monomer feed.

After 4 hours, the polymerization was stopped and propylene was separated by methanol and acetone treatment. The result of the polymerization test conducted using the catalyst component described in each Example under the above-mentioned conditions is shown in the table.

[Polymerization of Propylene in Liquid Monomers.]

The appropriate amount of catalyst component prepared according to any of the examples described above was suspended in a solution containing 5 mmol of aluminum trialkyl and 1.75 mmol of methyl para-toluic acid in 50 ml of n-heptane. This suspension was placed in a forced autoclave with a capacity of 3,000 ml containing an anchor-type magnetic stirrer and a thermostat thermometer at 60 ° C. under argon and containing 600 ml of propylene and hydrogen for a partial pressure of 0.2 atm.

After 4 hours, the reaction was stopped by removing the unpolymerized monomer and separating the obtained polypropylene. The results of the polymerization tests conducted using the catalyst components described in any of the examples under the above-described conditions are shown in Table IV.

[Polymerization of Propylene in Vapor Phase.]

Suspension containing 50 g of dry dry propylene in powder form in 50 ml of n-pentane, an appropriate amount of catalyst component prepared according to each of the above-described examples, and in addition, 5 mmol of aluminum triisobutyl and 1.25 mmol of methyl para-toluate. Together with a spiral screw stirrer and a thermostatically controlled thermometer at 60 ° C., a volume of 2,000 ml stainless steel autoclave was charged. The n-pentane was removed in vacuo and propylene was added to a partial pressure of 0.2 atm and hydrogen at a voltage of 15 atm. This pressure was kept constant throughout the prepolymerization reaction by continuing the monomer feed. After 4 hours, the polymerization was stopped and the polypropylene obtained was isolated.

The results of the polymerization tests conducted using the catalyst components described in the examples under the above-described conditions are shown in Table IV.

TABLE IV

Claims (1)

Halogenated Ti compounds soluble in hydrocarbons and having at least Ti-halogen bonds; Mg obtained by decomposition of an adduct between Mg dihalide and an electron donor selected from the group consisting of hydrocarbyl electron donor, ammonia, POCl ₃ and PSCl ₃ between 0.5 mol or more per mole of halide is A product consisting of a halide, wherein the decomposition of the adduct is reacted with an electron donor selected from the group consisting of an electron donor of the adduct and an organometallic compound of Group I-III metals or Si in the Mendeleev periodic table, and the adduct of the adduct is active When it contains a hydrogen atom, it is performed with a substance reacted with an electron donor selected from the group consisting of halides of tetravalent Si, trivalent halides of Al and B, and halides of Sn and Sb, and is normal in its X-ray powder spectrum. Instead of the maximum intensity line where Mg appears in the halide spectrum, the maximum intensity shifted by halo relative to the line described above It appears); And a catalyst component obtained by reacting an active hydrogen-free electron donor which can be reacted with a halogenated Ti compound or combined with a Mg halide-containing product prior to the reaction of the halogenated Ti compound with a Mg dihalide-containing product. It is composed of a cargo, a dihalide, a Ti compound, and a hydrocarbyl electron donor free of active hydrogen atoms, and the molar ratio of Mg / Ti in the catalyst component is 5 to 100 and the g mole of the electron donor is 1 g of Ti. The content of the Ti compound, which is 0.4 to 3.5 per atom and soluble in TiCl ₄ at 80 ° C present in the catalyst component, is in the range of 50% by weight or less based on the total content of the Ti compound. Solid catalyst component for superposition | polymerization of alpha olefins.