KR800000566B1 - Catalytic composition for polymerizing alpha-olefins - Google Patents

Abstract

Catalyst components for the polymn. of c>=3 α-olefins and their mixts. With ethylene are composed of an org. aluminum compd. contg. no halogen, an electron donor mixed with 15-100 wt% of the organoluminum compd. and a solid component contg. the reaction product of a Mg halide with a Ti(IV) compd. and the electron donor in which the mol ratio of electron donor/Ti is >=0.2, halogen/Ti>=4.

Description

Catalyst Composition for Alpha-olefin Polymerization

The present invention relates to a catalyst useful for the homopolymerization and copolymerization of alpha-olefins having at least three carbon atoms and to the polymerization of said alpha-olefins by mixing with ethylene.

In the polymerization of alpha-olefins, due to their high activity and high stereoregularity, the catalyst according to the present invention is particularly suitable for preparing crystalline polymers of alpha-olefins and crystalline copolymers of alpha-olefins and ethylene. .

Thus, another object of the present invention is to provide a method for producing the above crystalline polymer and copolymer.

More specifically, the present invention relates to a polypropylene having a catalyst and an isotacticity index and a crystalline copolymer of propylene and ethylene that can stereopolymerize propylene and a mixture of propylene and ethylene. It relates to a manufacturing method.

Examples of catalysts which exhibit high activity and high stereoregularity in the polymerization of alpha-olefins, in particular propylene, are described in British Patent 1,387,890 and German Patent Application DOS 2,504,036.

Catalysts described in British Patent No. 1,387,890 are generally reacted with a product obtained by finely pulverizing a halide in a mixture of an Al-trialkyl compound partially complexed with an electron donor compound with an electron donor compound and a halogenated Ti compound. Manufacture. The activity of these catalysts, expressed in grams of polymer per gram of Ti, is very high when performed in liquid phase in the absence of an inert hydrocarbon diluent.

In contrast, when the polymerization process is carried out in an inert hydrocarbon solvent, the activity is lowered to an unsatisfactory value in view of the necessity of purifying the polymer from the catalyst residue.

In addition, the stereospecific index of the polymers obtained with these catalysts is significantly reduced when the polymerization step is carried out using hydrogen as a regulator of the polymer molecular weight.

The catalyst described in DOS No. 2,504,036 is prepared by reacting a product obtained by reacting a liquid Ti compound with an Al-alkyl compound, a composition prepared by finely mixing a mixture of halides with an organic acid ester and an organic Si compound.

These catalysts exhibit high solid regularity when the polymerization is carried out in the absence of hydrogen, and on the contrary, when hydrogen is used as the molecular weight regulator, the catalyst is extremely reduced.

If an electron donating compound is added to an Al-alkyl compound used as a cocatalyst to attempt to increase the stereoregularity of the catalyst, a measurement of the stereospecific index of the polymer is obtained but the catalytic activity is considerably reduced.

Japanese Patent Application No. 49-25088 discloses a catalyst component prepared by pulverizing an Al-alkyl compound (Al-triethyl) and a mixture of MgCl ₂ with an organic acid ester and subsequently reacting the pulverized compound with TiCl ₄ . The obtained polymerization catalyst is described.

The catalyst described in this patent application specification has high activity and high solid regularity in the polymerization of propylene in the absence of hydrogen as a molecular weight regulator.

If the polymerization is carried out in the presence of hydrogen, the stereospecific index is severely reduced.

As a result of intensive studies, the inventors of the present invention also show high solid specificity when the polymerization is carried out in the presence of hydrogen in synthesizing a catalyst useful for polymerizing alpha-olefins and a mixture of the alpha-olefin and ethylene, and the polymerization is inert. It has been discovered how to produce high yields of polymers even when done in the presence of a hydrocarbon diluent.

The catalyst according to the present invention is obtained by contacting the following raw materials.

a) organometallic Al compounds which do not contain halogen atoms directly bonded to Al atoms,

b) an electron donating compound (e.g., Lewis base), used in an amount combining 15-100% of the organometallic Al compound with an electron donating compound,

c) a reaction product of at least a halogenated Mg compound and a tetravalent Ti compound and a reaction product of an electron donor compound on the surface, wherein the reaction product has a molar ratio of electron donor compound / Ti of 0.2 or more and a halogen atom / The ratio of Ti is at least 4, at least 80% by weight of the tetravalent Ti compounds contained in this product are insoluble in boiling n-heptane and at least 50% by weight of Ti compounds insoluble in boiling n-heptane at 80 ° C. A solid characterized by being not only insoluble in titanium tetrachloride, but also insoluble in titanium tetrachloride at 80 ° C., as well as the surface area of component c) of at least 20 m ² / g, preferably at least 40 m ² / g. ingredient.

The catalyst of the invention is preferably prepared by contacting component c) with a product obtained by premixing component a) and component b) for a period of generally up to 1 hour. Highly practical catalysts can also be obtained by mixing these components simultaneously, or by first contacting component c) with component a) and then with component b) or in reverse order. The amount of the electron donating compound used as component b) preferably has a molar ratio between the organometallic Al compound and the electron donating group of the electron donating compound reacting with the total amount of the compound in the range of 0.2 to 0.4. This means that 20-40% of the organometallic Al compound is combined with the electron donating compound.

으로)전자공여 화합물(또는 루이스염기)은 성분 b)으로서 사용될 수 있다.It is possible to provide a complex with the organometallic Al compound used as component a) or to cause a substitution reaction with such a compound (e.g.,

The electron donating compound (or Lewis base) can be used as component b).

Examples of electron donating compounds which can be used as component b) include amines, amides, ethers, ketones, nitriles, phosphines, stybins, arsines, phosphoamides, thioethers, thioesters, aldehydes, And salts of alcoholates and organic acids with metals belonging to groups I to IV of the periodic table. In the case of Al salts, they may be formed by reaction of the organic acid with the organometallic compound originally used as component a).

Suitable organic acids include aromatics such as benzoic acid and peroxybenzoic acid.

Examples of specific compounds include triethylamine, N, N'-dimethylpiperazine, diethyl ether, di-n, butyl ether, tetrahydrofuran, acetone, acetophenone, benzonitrile, tetramethylurea, nitrobenzene, Li-butyl And dimethylaminophenyl-lithium and Na-dimethylamide.

The most interesting results for both the activity and stereoregularity of the catalyst are achieved with esters of organic and inorganic oxygen containing acids and ethers such as di-n-butylether. Examples of particularly suitable esters are alkyl esters of aromatic acids such as benzoic acid, p-methoxy- or ethoxybenzoic acid and p-toluic acid, for example ethylbenzoate, ethyl p-methoxy-benzoate, methyl p-tolu And ethyl p-butoxy benzoate.

Other examples of useful esters include diethyl carbonate, triethyl borate, ethyl pivalate, ethyl naproate, ethyl o-chlorobenzoate, ethyl acetate, dimethyl maleate, alkyl or aryl silicates, methyl methacrylate. I can lift it.

Al(C1₂H₂₅)₃과 같은 Al-트리알킬 화합물을 들 수가 있다.Examples of suitable organometallic Al compounds which can be used as component a) include, for example, Al-triethyl, Al-tripropyl, Al-triisobutyl,

Al-trialkyl compounds like Al (C1 ₂ H ₂₅ ) ₃ can be mentioned.

Organometallic Al compounds containing two or more Al atoms bonded via O or N atoms may also be used. These are generally obtained by reacting Al-trialkyl compounds with water, ammonia or primary amines by known methods.

Examples of such compounds include the following.

Another example is the organometallic Al compound described in Italian Patent Application No. 24287A / 75.

Examples of other useful compounds include hydrides of aluminumdialkyl, alkoxides of aluminum-dialkyl such as Al (C ₂ H ₅ ) ₂ (OC ₂ H ₅ ), Al (C ₄ H ₉ ) ₂ (OC ₄ H ₉ ) And sesquialkoxides of Al-alkyl such as sesquiethoxy aluminum-ethyl and sesquibutoxy aluminum butyl.

The electron donating compound present in the bound form in component c) may be the same compound as used in component b) or as a different compound.

In this case, an electron donating compound capable of forming a complex with Mg halogen wave can be used to prepare component c).

Preference is given to using esters, ethers and diamines. As examples of the esters, those mentioned above which can be used as catalysts as component b) can be used.

Particularly effective diamines include N, N, N ', and N'-tetramethylethylenediamine.

Component c) of the present invention is a halogenated Mg compound selected from Mg dichloride and dibromide and halogenated compounds of tetravalent Ti, in particular TiCl ₄ , TiBr ₄ Tihalogen-alcoholates and organic acid esters, especially aromatic acids, at least on the surface For example, it is preferable to contain a reaction product with an electron donating compound selected from esters of benzoic acid. The nature and composition of this component are redefined by the following parameters.

The Mg / Ti ratio is between 3 and 40, preferably between 10 and 30, the halogen atom / Ti ratio is between 10 and 90, preferably between 20 and 80, and the molar ratio of the electron donating compound / Ti is 0.2 or more. In particular, 0.4-3 phase is more preferably between 1.2 and 3 phases.

At least 80% by weight, preferably 90% by weight, of the Ti compound contained in component c) is insoluble in boiling n-heptane and, on the other hand, at least 50% by weight of Ti compound insoluble in boiling heptane, more specifically 70 At least% by weight is insoluble in titanium tetrachloride at 80 ° C.

Component c) surface area of the insoluble product in titanium tetrachloride in surface area and 80 ℃ of generally in the range between 100m ² / g or more, particularly 100~200m ² / g.

Particularly suitable for the preparation of catalysts which are highly active and at the same time high stereoregularity, component c), when defined chloride and bromide according to ASTM 3-0854 and 15-836, is the most common in the spectrum of the normal form of Mg chloride and bromide. Dense lines show reduced relative strength and asymmetrically expand, thus forming a halo representing intensity peaks shifted with respect to the distance d between the lattice planes of the maximum strength lines, or the spectrum is defined as the maximum The intensity line no longer exists and instead the halo is specified by the spectrum with the intensity peak shifted with respect to the distance d of the line.

With respect to MgCl ₂ , halo intensity peaks were compared between d = 2.44 and 2.97 kPa.

In general, the composition of component c) is 70-80% by weight of Mg dichloride or dibromide, the remaining components minus 100, consisting of Ti compounds and electron donating compounds.

However, component c) may contain inert solid fillers in addition to the above components and in an amount of at least 80% by weight of component c).

Examples of such materials include LiCl, CaCO ₃ , CaCl ₂ , Na ₂ SO ₄ , Na ₂ CO ₃ , Na ₂ B ₄ O ₇ , CaSO ₄ , AlCl ₃ , B ₂ O ₃ , Al ₂ O ₃ , SiO ₂ , TiO _2, etc. can be mentioned.

In particular, it should be noted that if component c) is prepared in the presence of an inert solid material, the surface area is generally reduced.

More specifically, it has been found that when component c) is uniformly mixed with flocculants, in particular B ₂ O ₃ , AlCl ₃ and the like, the resulting product generally has a surface area of 10-20 m ² / g or less.

However, the execution of the catalyst obtained from component c) thus treated is particularly acceptable in terms of polymer yield.

In the preparation of component c), the active components of component c) can be supported on inert carriers such as SiO ₂ and Al ₂ O ₃ with high porosity. In this case, the Ti and Mg halogenated compounds and the electron donating compounds are constituted in a reduced proportion based on their total amount, so that a catalyst having a minimum amount of unnecessary substances such as halogen can be obtained.

Note that although the ratio of Mg / Ti in component c) is generally 1 or more, this ratio is 1 or less when using TiO ₂ and similar Ti compounds which do not react with halogenated Mg compounds as fillers.

The general method starts with a specific composition or carrier containing Mg halides and complexes of Mg halides and electron donating compounds, wherein the molar ratio of Mg) / electron donating compound in the composition is at least 2, preferably from 2 to 15 A Ti compound wherein the composition or carrier is treated with a tetravalent liquid Ti compound under conditions in which a fixed amount of the Ti compound is immobilized on the carrier, and then soluble in boiling n-heptane and extracted with titanium tetrachloride at 80 ° C. The reaction solid product is separated from the liquid phase under conditions that do not actually remain in the product.

The characteristics of the carrier to be treated with the liquid Ti compound are shown in the X-ray spectrum, where the maximum dense lines appearing in the normal form of the Mg halide spectrum show a relatively reduced intensity and an asymmetrically diffused state, resulting in a peak of intensity peaks. It forms a halo with an intensity peak shifted with respect to the maximum dense line, or no maximum dense line exists in the spectrum, but instead shifted with respect to the distance of the maximum dense line.

This carrier, a raw product for the preparation of component c), can be obtained in several ways. Suitable methods include X-rays of the above-mentioned halo-powdered products, which have powdered Mg halides, in particular dichlorides and mixtures of dibromide and electron donating compounds, and have a peak of intensity shifted with respect to any maximum dense line. Until indicated in the spectra, the reaction is in the presence of a substance which may contribute to promoting the powdering, such as Ti compounds and / or inert carriers and / or silicone oils.

The powdered compound is then treated with a liquid halide Ti compound, in particular TiCl ₄ , for a time sufficient to fix an appropriate amount of the Ti compound at a temperature between room temperature and 200 ° C.

The solid product of the reaction is then separated from the liquid phase by means of filtration, precipitation, etc. under conditions of dilution with temperature and / or liquid Ti compounds, and in the case of solid products, first with boiling n-heptane and then with 80 Extraction with TiCl ₄ at < RTI ID = 0.0 > C < / RTI > no more than 20 wt% and 50 wt% of extractable Ti compounds, respectively.

Other methods of preparing a carrier suitable for preparing component c) include reacting anhydrous Mg halide and an organic compound containing active hydrogen in the presence of an organic acid ester in an inert hydrocarbon solvent and converting the reaction product into an organometallic Al compound. To continue processing.

The order of the reaction may be reversed, i.e., a complex of Mg halide and an active hydrogen-containing compound is reacted with an organometallic compound and then the product is reacted with an organic acid ester.

This manufacturing method is described in Japanese Patent Application No. 49-100553.

The product thus obtained is washed with an inert hydrocarbon solvent to remove traces of organometallic compounds, followed by reaction with liquid Ti compounds, in particular TiCl ₄ , at temperatures between 20 and 200 ° C., followed by boiling of solid phase reaction products. The Ti compound, which can be extracted with titanium tetrachloride at 80 ° C. using n-heptane, is separated from the liquid phase under conditions such as filtration or precipitation until no Ti compound remains in the solid phase component.

Other methods of preparing a carrier suitable for the preparation of component c) are described in Japanese Patent Application No. 50-17934. In this case, too, the carrier is reacted with the liquid Ti compound, and the reaction product is separated from the liquid phase under the condition that no soluble Ti compound remains in the solid product while boiling heptane and titanium tetrachloride at 80 ° C.

According to the above-described various kinds of preparation, when using Mg halide, in particular when produced by pulverization of the catalyst component, which is preferably used in this anhydride (H ₂ 0 content is less than 1% by weight) available form.

However, hydrates of Mg halides usually containing 0.1 to 6 mol of H ₂ O per mol of halide can be used as raw materials for the preparation of component c). In addition, oxygen-containing Mg compounds such as MgO, Mg (OH) ₂ , Mg (OH) Cl, Mg carbonate, Mg salts of organic acids, Mg silicates, Mg aluminates, Mg alcoholates and halogenated derivatives of the foregoing compounds I can lift it. Mg-C binding materials containing organometallic Mg compounds can also be used. Examples of such compounds include Grignard reagents and compound MgR ₂ , wherein R is an alkyl-, cycloalkyl- or aryl group containing up to 20 carbon atoms. In all cases, the Mg compound is reacted with excess titanium tetrachloride, which is preferably heated and separated at the boiling point of titanium tetrachloride and then at the TiCl ₄ boiling point to obtain a solid phase product.

The resulting solid product is treated by suspending an inert hydrocarbon and an organic acid ester, particularly an ester of an aromatic carboxylic acid, in an amount of about 1-20 mol per g atom of Ti contained in the carrier, and the reaction temperature at this time is from room temperature to 200 It shall be between ° C.

The solid product treated in this way is precisely separated from the unreacted ester and then reacted with the liquid halide Ti compound and then separated from the reaction liquid phase under certain conditions as described in other preparations.

In these production methods, at least 80% by weight of the Ti compound contained in component c) is insoluble in boiling n-heptane and 50% by weight or less of the Ti compound insoluble in boiling heptane is extracted with titanium tetrachloride at 50 ° C. It is important. Indeed, the presence of soluble Ti compounds is not beneficial both in the activity and stereoregularity of the catalyst, especially when the polymerization is carried out in the presence of hydrogen.

The catalysts according to the invention are particularly useful in the preparation of polymers of alpha-olefins having at least three or more carbon atoms, in particular crystalline polymers and copolymers of propylene. They can also be used for the polymerization of ethylene, in which case component b) can be omitted. It can also be used as a catalyst component having the good properties of component c), where it has been found that the valence tetravalent Ti is reduced to valence below 4 by treating component c) with a reducing agent before contacting component a). Examples of suitable reducing agents include organometallic Al compounds, Al metals, and hydrogen.

The polymerization is carried out by a conventional method, and the polymerization reaction is carried out in the liquid phase in the presence or absence of an inert hydrocarbon such as hexane, heptane, cyclohexane and the like or in the gas phase.

The polymerization temperature is generally between 0-150 ° C., preferably between 40-90 ° C., and is carried out at atmospheric pressure or higher.

When preparing a crystalline copolymer of propylene, propylene is polymerized until an amount of homopolymer of about 60 to 90% of the total composition is obtained, and then propylene-ethylene mixture or ethylene alone is polymerized in at least one polymerization step. Preferably, the ethylene content is in the range of 5-30% based on the weight of the final composition. In addition, polymerization of a mixture of propylene and ethylene yields a copolymer containing only 5% by weight of ethylene.

Hereinafter, the present invention will be described in detail by way of examples.

[Examples 1-11 and Comparative Examples 1-2]

A) Powdered.

3kg 및 18kg을 포함하고 있는 N.V.TEMA′S Gravenhage(Holland)가 제작한 VIBRATOM형의 2개의 진동 분쇄기 중에서 동시에 분말화시켰다.Anhydrous MgCl ₂ (moisture content 1 wt% or less), ethylbenzoate (EB) and optionally silicone, stainless steel balls having a total capacity of 1 and 6 L and a diameter of 16 mm, respectively

Powders were simultaneously powdered in two vibratory mills of type VIBRATOM manufactured by NVTEMA'S Gravenhage (Holland) containing 3 kg and 18 kg.

The pulverization was carried out at a grinder internal temperature of 40 ° C. using a filling factor of about 135 g per liter of the total capacity (vacuum), varying the grinding time in each step at different times, that is, in the range of 50 to 100 hours.

The filling (continuous powdering) of the mill of the product to be powdered and the extraction of the powdered product are carried out in the presence of nitrogen.

In Example 10, powdering was carried out in a bowl mill containing 120 stainless steel balls with a capacity of 1 L and 15.8 mm in diameter, and spun at 50 rpm.

Table 1 below shows data related to the type and amount of the product to be powdered, the powdering conditions and the properties of the product in various tests.

B) Treatment with TiCl ₄

At the same time a portion of the powdered product (15-50 g) was transferred to a 500 cc reactor which was always in contact with excess TiCl _{4 in the} presence of nitrogen. Treatment with TiCl ₄ was carried out at a temperature between 80 and 135 ° C. for 2 hours, after which excess TiCl ₄ and the product soluble therein were removed by filtration at the specific temperatures listed in Table 1. Then washed twice with boiling hexane. The resulting solid product was dried in a nitrogen atmosphere and a portion thereof was analyzed to examine the content of Ti and Cl (%).

The data according to the operating conditions used in the various tests during the treatment with TiCl ₄ and the characteristics of the solid product thus obtained are also shown in Table 1.

The stereoregularity and activity of these solid products (catalyst components) were examined by polymerization of propylene in hydrocarbon solvents or liquid monomers using aluminum-trialkyl, a cocatalyst treated with an electron donor compound.

C) polymerization in solvent

A stirrer was installed and polymerization was carried out in a 2,500 cc autoclave previously purged with nitrogen at 60 ° C. The polymerization was carried out at a temperature of 60 ° C. for 4 or 5 hours at a propylene (C ^- ₃ ) effective pressure of 5, 8 or 9 (addition of propylene during the polymerization test and kept constant).

As the hydrocarbon solvent, n-heptane (nC ⁺ ₇ ), hexane (C ₆ ⁺ ), or heptane (C ₇ ⁺ ), which had been technically deodorized and made anhydrous (1,000 cc), was used. It carried out in the presence of hydrogen which is a molecular weight regulator.

Al (C ₂ H ₅ ) ₃ (TEA) or Al (iC ₄ H ₉ ) ₃ (TIBAL) is used as the aluminum trialkyl, and p-ethylanisate (PEA) and ethyl p-toluate ( EPT). The molar ratio between Al-trialkyl and the electron donating compound ranged from 2.74 to 3.14.

Solvent (870 cc) in autoclave in the presence of propylene. A catalyst component suspended in a portion of Al-alkyl and an electron donor compound premixed in 150 cc of this solvent for 10 minutes, and at the same time in 80 cc of a solvent containing the balance of Al-alkyl and an electron donor compound was sequentially charged. Then, hydrogen and propylene were introduced into the autoclave until the polymerization pressure was reached, and the temperature was raised to a predetermined temperature.

At the end of the polymerization test, the solvent was removed by steam and the polymer thus obtained was dried in the presence of nitrogen at 70 ° C.

D) Polymerization in Liquid Monomers

This polymerization was carried out at 26.5 effective pressure of propylene for 5 hours at a temperature of 65 ° C in the presence of hydrogen (15Nl and 50Nl) as molecular weight regulator in 30-1 and 135-1 high pressure cookers equipped with agitators. The amount of Al (C ₂ H ₅ ) ₃ 12.5 g (tested in a 30-1 autoclave) and Al (iC ₄ H ₉ ) ₃ 36 g (tested in a 135-1 autoclave) is in a molar ratio between 2.2 and 2.74 Treated with an electron donating compound such as p-ethylaniate or ethyl p-toluate was used as Al-trialkyl.

The autoclave was infused with Al-alkyl, liquid propylene and electron donating compound in 12 wt% heptane solution in the presence of propylene.

The autoclave was heated to medium pressure and then the catalyst component and hydrogen were introduced therein.

At the end of the polymerization, the remaining propylene was evaporated and the polymer was then dried at 70 ° C. in the presence of nitrogen.

In both cases (polymerization in solvent and liquid monomer), the dry polymer is weighed to calculate the yield for titanium present in the catalyst, and the polymer is extracted with boiling n-heptane to purge the insoluble polymer in boiling n-heptane. The amount of cents was measured.

Thus the apparent density and intrinsic viscosity value (in tetralin at 135 ° C.) of the polymer were also measured. Table 2 below shows the data relating to the various polymerization tests and the properties of the polymers thus obtained.

TABLE 1

( ^* ) Spectra A shows that the maximum strength line of magnesium chloride at d = 2.56Å is reduced and asymmetrically expanded in the comparative strength to form halo, and its peak is between d = 2.44Å and d = 2.97Å. Means spectrum.

Spectrum B takes a halo with an intensity peak that is absent and instead changes with respect to such a maximum intensity line, and has a spectrum whose intensity peak is between d = 2.44 Pa and d = 2.97 Pa. it means.

( ^** ) PDSM 500, PDSM 100 and PDSM 50 are polydimethylsiloxanes with viscosity 500, 1,000 and 50 centistokes, respectively.

TABLE II

Example 12

Anhydrous MgCl ₂ (containing less than 1% by weight of H ₂ O) was triturated with the electron donating compounds shown in Table 3 under the conditions used in Example 4. The milled product was treated with TiCl ₄ under the conditions of Example 4. The reaction product thus obtained showed Cl and Ti contents shown in Table 3.

Used for the polymerization test under the conditions described in the above-mentioned catalyst component in Example 8, but the difference is only one C ₃ to the effective pressure 5.43atm.

Data and stereospecific indices relating to polymer yields are shown in Table 3.

TABLE 3

EPT = ethyl p-toluate

PEA = p ′ ethylanisate

MB = methylbenzoate

MMA = methyl methacrylate

NBE = di (n'butyl) -ether

Example 13

500 ml of ketocin was introduced into a flask equipped with a stirrer.

Propylene was introduced at a rate of 30 l / hr for 1 hour to expel air and moisture.

2.5mMol of Al-triethyl and 0.884mMol of the electron donating compound shown in Table 4 were introduced into the flask at room temperature. After 5 minutes, the catalyst component prepared in Example 7 was introduced, except that the only difference was the use of silicone oil having a viscosity of 20 cm stoke at 20 ° C. The molar ratio of Al / Ti in the catalyst was 2.5.

The mixture was heated at 60 ° C. and propylene was polymerized at atmospheric pressure for 1 hour to introduce a ratio to maintain a constant pressure during polymerization. Thereafter, propylene was replaced with nitrogen, and the reaction mixture was cooled to room temperature. The solid product was filtered off and then washed twice with dry methanol at 70 ° C. The kerosene layer in the filtrate was evaporated to recover the soluble polymer. Data and total stereospecific indexes relating to the yield of polymers are shown in Table 4.

TABLE 4

BA = Benzoic Acid

POBA = peroxy-benzoic acid

ACC = alpha-aminoacetic acid

BAA = Benzoic Acid Amide

NBE = di (n.butyl) -ether

Example 14

10 g of the catalyst component containing 2.1 wt% Ti prepared in Example 13 was suspended in 150 ml of kerosene. 2.2 mmol of diethylaluminum chloride diluted with kerosene was added at room temperature, followed by 2.2 mmol of ethylbenzoate, and the mixture was stirred for 1 hour. The solid product was filtered off with hexane and dried in vacuo.

Into a 2 liter autoclave filled with 3.75 mmol of Al (C ₂ H ₅ ) ₃ pre-mixed with 750 ml of n-hexane and 1.25 mmol of methyl p-toluate, an amount of dried product corresponding to 0.03 mmol / l Ti was introduced. It was.

The polymerization test was carried out at 60 ° C. for 4 hours at 400 ℓ of hydrogen at 8 atm pressure of propylene.

After filtration to remove the solid and dried, 225.9 g of powder were obtained, its stereospecific index being 94.2.

From this filtrate, 5.9 g of a soluble polymer was recovered in n-hexane.

Example 15

10 g of MgCl ₂ containing less than 1% by weight of water and suspended in kerosene (100 ml) was treated with 18.4 ml of ethyl alcohol at 20 ° C. for 2 hours. The complex of MgCl ₂ with ethanol was mixed with 2.5 ml of 2, 6-dimethylphenol for 1 hour at 20 ° C., 11.7 ml of ethyl-benzoate for 1 hour at 80 ° C., and Al (C ₂ H ₅ ) for 2 hours at 20 ° C. _The reaction was carried out in the order of 2Cl 22.9ml.

Solid product was separated by filtration, n. Washed with hexane and dried in vacuo. 10 g of this product were treated with 100 ml of TiCl ₄ at 100 ° C. for 2 hours. Excess TiCl ₄ was isolated by filtration. The solid product was washed repeatedly with n-hexane and then dried in vacuo.

As a result of analyzing the product, the following results were obtained.

Ti = 3.60 wt%

Cl = 58.0 wt%

Under the conditions used in Example 14, 31 mg of solid product was used in the polymerization test. Filtration removed the solvent and evaporated to give 130 g of polymer. The stereospecific index of this polymer was 95.4. 30 g of the soluble polymer was recovered from the filtrate.

Example 16

[Chemical preparation]

Anhydrous ₁ kg MgCl ₂ , 0.23 L ethylbenzoate and 0.15 L PDMS * were placed in a 100 L vibration mill (each with 350 kg of stainless steel balls 15 mm in diameter), where they were contacted with each other at 70 ° C. for 120 hours.

500 g of the co-grinding product thus obtained was suspended in 5 L of TiCl ₄ , and the resulting suspension was reacted at 80 ° C. for 2 hours. After completion of the reaction, the production system was filtered at the same temperature to recover its solid component, which was then washed thoroughly with hexane until no further TiCl ₄ was detected.

The resulting solid phase component contained 2.0, 23.0 and 64.0 weight percent Ti, Mg and Cl as atoms, and 10.5 weight percent ethyl benzoate and exhibited a specific surface area of 200 m ² / g.

^* 50 cm Stokes of polydimethylsiloxane viscosity

[polymerization]

Four reactors in series: reactors A, B, D and E (effective volumes 190, 120, 140 and 200 l respectively) and fresh drum C (effective volume 30 l) installed between reactors B and D were installed. Used.

Reactor A was charged with 0.75 mmol Ti / hr as the hexane slurry of the solid CAT component prepared as described above, and the Al / Ti and Al / EPT molar ratios were 50 and 2.75, respectively, and the total amount of hexane was 2.1 L / hr. .

The reactor was also charged with propylene 7 Nm ³ / hr and hydrogen 13 Nl / hr, while maintaining the reactor pressure at 7 kg / cm ² gauge and the polymerization temperature at 60 ° C.

As a result, PP ^** having a stereospecific index and Ml ^*** of 92.8% and 0.36, respectively, was prepared in Reactor A at a rate of 240,000 g-pp / g-Ti.

^** Polypropylene

^*** Melt Index

The polymer slurry discharged from reactor A was then sent to reactor B, which was again charged with triethyl-Al 4.5 mmol / hr and hexane 5Nl / hr. The polymerization in Reactor B was then carried out at 3.0 kg / cm ² G pressure and polymerization temperature of 60 ° C.

PP with stereospecificity index 92.2% and MI 0.32 was prepared in reactors A and B at a rate of 290,000 g-PP / g-Ti.

The polymer slurry discharged from reactor B is then sent to flashdrum C, from which unreacted propylene monomer is removed, which is then sent to reactor D, where ethylene 1,000 Nl / hr and 80Nl / hr hydrogen are reacted. Was supplemented with nitrogen gas to induce 2.5 kg / cm ² G.

The composition of the gas held in reactor D was 7.3% hydrogen, 45.5% nitrogen, 25.8% ethylene, 0.9% propylene and hexane.

As a result of polymerization in Reactor D at a polymerization temperature of 60 ° C., a polymer having its Ml value of 0.29 and a packing density of 0.350 was obtained at a rate of 27,000 g-weight / g-Ti.

Then, the polymer slurry discharged from reactor D was sent to reactor E, where 1,700 Nl / hr of ethylene, 70 Nl / hr of hydrogen, 4.5 mmol hr of triethyl-Al, and additionally hexane of 10 L / hr were added. Supplied.

The polymerization was carried out at a polymerization pressure of 2.0 kg / cm ² -G and a polymerization temperature of 60 ° C. The composition of the gas held in reactor E was 38.2% hydrogen, 3.4% nitrogen, 35.6% ethylene, 0.1% propylene and 22.6% hexane. .

As a result of polymerization in Reactor E, a polymer having an Ml value of 0.24 and a packing density of 0.350 was prepared at a rate of 24,000 g-polymer / g-Ti. The polymer thus prepared contained a 17.6 ratio of ethylene polymers per PP100 weight ratio.

Claims (1)

Metal Al halides (a) containing no halogen atoms directly bonded to Al atoms, electron donating compounds (b) in an amount mixed with 15 to 100% of the organometallic halides, and at least halogenated Mg compounds on the surface Containing a reaction product of a tetravalent Ti compound and an electron donor compound, wherein the molar ratio of electron donor / Ti in the product is at least 0.2, the molar ratio of halogen atoms / Ti is at least 4, and the tetravalent Ti contained in the product insoluble in boiling n- heptane insoluble Ti compound in a 50% by weight or more are also insoluble in a 80 ℃ TiCl ₄ insoluble in the product to the TiCl ₄ is 80 ℃ eseo in boiling n- heptane is 80% or more by weight of the compound of the mixture of the olefin, or a ethylene-surface area and its surface area is 40m ² / g or more of solid component (c) of the alpha carbon atoms are more than two is characterized by consisting of a product obtained by contacting the components of the mixed raw material Catalyst composition.