FI57601C - SAETT ATT HOMOPOLYMERISERA ELLER SAMPOLYMERISERA ETHLEN PROPYLEN EN BLANDNING AV ETHLEN ELLER EN ANNAN ALFA-OLEFIN - Google Patents

Description

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(32) (33) (31) Requested «uolkeui — Begird prlorltet 10.11.72 27.12.72 Japan-Japan (JP) 112151/72, I3OO52 / 72 Proven-Styrkt _ (71) Mitsui Petrochemical Industries, Ltd., 2- 5, 3-chome, Kasumigaseki,

Chiyoda-ku, Tokyo, Japan-Japan (JP) (72) Norio Kashiva, Ivakuni-shi, Yamaguchi-ken, Japan-Japan (JP) (7 ^) Oy Kolster Ah (5! +) Method of homopolymerizing or copolymerizing ethylene, propylene, a mixture of ethylene and another β-olefin, a mixture of ethylene or propylene and a diolefin or a mixture of ethylene, another β-olefin and a diolefin and the catalyst composition used therein - Sätt att homopoly-merisera eller sampolymerisera ethyl, propylene The present invention relates to a process for the polymerization or copolymerization of olefins, which yields a catalyst complex for the polymerization or copolymerization of olefins, which can be converted to olefins or a diolefin. , which is advantageous both economically and in terms of product quality, and which process uses a more efficient catalyst composition to obtain polymers with the desired particle size and range an narrow particle size distribution. This method is very suitable for use in continuous polymerization processes.

Previously, GB Patent 1,256,851 proposed a transition metal-based catalyst component for obtaining polyolefins having a wide molecular weight distribution for use as a solid reaction product prepared in 2,57601 by reacting a solid support consisting of a partially hydrated oxalogen, a divalent metal halide such as magnesium halide, oxide, complex oxide, complex hydroxide, alcoholate, salt of inorganic oxygen acid or mono- or polycarboxylic acid salt of divalent metal with organoaluminum compound or organomagnesium compound, separation of the resulting solid from this reaction product system. According to this patent, it is essential to separate the solid reaction product from the product obtained by reacting the support with an organometallic compound. It is further necessary that the separated solid reaction product be washed as an inert solvent and then dried, and that the reaction of this product with the transition metal compound be carried out in such a way that no small amount of diluent is present. Thus, the disadvantage of this method of preparing the catalyst component is that the finely divided solid is separated and washed without coming into contact with air or moisture, and then completely dried.

According to BE patent 767 586, published November 25, 1971, a solid support corresponding to the formula nM (0R) n, where X is a monovalent inorganic group, in particular a halogen atom, M is a divalent metal atom such as Mg and R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and 04 n = 2, is reacted with an organoaluminum compound represented by the formula AIR ', wherein Y' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen atom and a solid product is separated from the reaction product, and the separated product is reacted with a halogen derivative of a transition metal in the absence of a liquid diluent, after which the solid product is separated from the reaction product and the obtained compound is used as a transition metal catalyst component according to the above patent. The preparation of such a transition metal catalyst component is complicated and requires careful work.

It has also previously been proposed in GB 929 969 to prepare a polyolefin, in particular a polypropylene with excellent stereospecificity, by steam polymerization using as a catalyst component a reaction product prepared by reacting a solid support, for example CaCO 2, CaCl 2 or NaCl with organo 57601 subsequently obtained reaction product with a transition metal compound. According to this proposal, it is essential that the above-mentioned catalyst component be heat-treated, and if this heat treatment is omitted, the obtained catalyst component cannot produce polymers having good stereospecificity. In addition, the catalysts prepared according to this proposal have very poor activity.

DE-A-2,111 k35 discloses a titanium catalyst component prepared by reacting magnesium alcoholate with an acid halide (including SiCl 2), after which the product thus obtained is reacted with a titanium compound. Said DE patent does not disclose or suggest an addition compound (i) or a magnesium halide according to the invention.

Studies have now been carried out to develop catalysts which are very suitable for the polymerization or copolymerization of olefins and it has been found that high activity catalysts can be used to produce polymers of the desired particle size and particle size distribution, and that these catalysts are very suitable for continuous polymerization. These catalysts can be prepared without having to perform the above-mentioned complex control procedures or heat treatment of the catalyst component, as in the previous processes described above. It has been found that the process can be improved by using a reaction product obtained from a magnesium dihalide donor adduct, a Si or Sn compound which is a halogen compound of Si, a halogen compound of Sn, an organohalogen compound of Si or an organohalogen compound of Sn, and by using titanium or vanadium compounds as a transition metal catalyst component.

The improvements which are the subject of the present invention cannot be obtained, as can be seen from the comparative examples below, if catalysts which are organo-Si compounds or organo-Sn compounds belonging to Group IV metal compounds of the Periodic Table and a solid reaction product which is obtained by reacting the separated reaction product formed instead of the compound Xg ^ MgCOR) ^ according to the above-mentioned second proposal, by reacting the magnesium dihalide donor adduct and the compound AIR1 Y_ with the halogen derivative of the transition metal P 3 "p ^ without the presence of a diluent.

It is therefore an object of the present invention to provide an improved process for polymerizing or copolymerizing olefins. Another object of the present invention is to provide a catalyst composition suitable for the above process.

Many other objects and advantages of the present invention will become apparent from the following description.

The process of this invention homopolymerizes or copolymerizes ethylene, propylene, a mixture of ethylene and another olefin, ethylene or. a mixture of propylene and diolefin or a mixture of ethylene, another X-olefin and diolefin in the presence of a catalyst consisting of a) a transition metal catalyst component prepared by reacting a titanium or vanadium compound with a solid magnesium compound support, and b) an organometallic compound which compound is a compound of a metal belonging to Periodic Group I-III of the system, preferably an organoaluminum compound.

Examples of other o <-olefins or diolefins are propylene, butene-1, hexene-1, methylpentene-1, octene-1, butadiene, isoprene, ethylidene norbornene, dicyclopentadiene and 1,1 + hexadiene.

When polymerizing olefins using the catalyst of this invention, the amount of polymer obtained per unit weight of the transition metal atom becomes larger, and the amount of polymer obtained per unit weight of the support also increases (the weight of the transition metal compound on the support can be ignored along with the weight of the support). As a result, the halogen content of the polymer caused by the carrier can be significantly reduced. In addition, since the diameter of the obtained polymer particles is in the desired range and the polymer is of uniform quality, the formation of large, coarse polymer particles can be prevented, which cause bad disadvantages during continuous polymerization while preventing the formation of very fine polymer particles.

In addition, since the catalyst system contains as a component a supported transition metal compound prepared in accordance with the present invention, a very large amount of polymer per unit weight of transition metal compound or support is obtained even when the catalyst removal step is completely eliminated from the polymerization process and no problems are encountered. , such as discoloration of the polymer or rusting of the mold during the manufacturing process due to halogen remaining in the polymer. In addition, the molecular weight distribution of the polymer becomes wider than if no silicon or tin halogen compound or organohalogen compound is used in the preparation of the catalyst. Thus, polymers having good flow properties during preparation can be prepared. The solid support to be used in this invention is with a magnesium dihalide such as dichloride, dibromide, diiodide or difluoride, with magnesium dichloride and magnesium dibromide being most preferred.

5,57601

The properties of the resulting catalyst can be varied to some extent depending on the type and amount of donor. In general, it is recommended that the donor be added in an amount of 0.1 to 10 moles per mole of magnesium dihalide. In the preparation of a titanium catalyst component having a good catalyst system activity which makes it possible to omit the treatment of the catalyst residue after polymerization, the donor is preferably used in an amount of at least 1+ moles, most preferably at least 6 moles per mole of magnesium dihalide.

Anhydrous magnesium dihalide is usually used. As used herein, the term "anhydrous" does not exclude from its scope the use of commercial grades of reagents sold "anhydrous" and containing very small amounts of moisture.

If the amount of donor is too small, the polymerization activity per unit amount of titanium or vanadium atom of the catalyst is low and the catalyst undesirably gives the polymers as coarse or ultrafine particles with an uneven particle size distribution. With the donor, the magnesium dihalide particles become finer as a result of the pretreatment than before the treatment, and the infrared absorption spectroscopic analysis and X-ray analysis of the product show that the product has become an adduct of magnesium dihalide and donor. The reaction of the magnesium dihalide support with the donor is usually carried out, for example, at a temperature between -10 and + 100 ° C. The reaction proceeds satisfactorily at room temperature. Most usually the reaction temperature is 0-100 ° C, preferably 10-60 ° C. In any case, the temperature used is such that the adduct obtained does not decompose or convert to other compounds. The reaction time is usually 10 minutes to 2 hours. The reaction is usually carried out under a nitrogen atmosphere in an inert orgasmic medium. Examples of media include those used in the polymerization and include hexane, heptane, kerosene, benzene, xylene, and fluorobenzene.

The alcohol adduct of magnesium dihalide is prepared by other conventional methods. It can be prepared, for example, by reacting metallic magnesium with ethanol containing dry hydrochloric acid to form MMgCl 2 .EtOH / Russian Journal of Inorganic Chemistry, Vol. 12, No. 6, 901 (1967).

Donors for use in the present invention include water, saturated or unsaturated aliphatic alcohol containing 1 to 12 carbon atoms, saturated or unsaturated aliphatic carboxylic acid containing 1 to 12 carbon atoms, saturated aliphatic carboxylic acid having 1 to 12 carbon atoms, and 1 to 2 carbon atoms. ester of a saturated aliphatic alcohol, an ester of a saturated aliphatic carboxylic acid having 1 to 12 carbon atoms β 57601 and an ester of an unsaturated aliphatic alcohol having 2 to 12 carbon atoms, an ester of 3 to 12 carbon atoms, an unsaturated aliphatic carboxylic acid having 1 to 12 carbon atoms, and 1 to 12 carbon atoms Ester of an unsaturated aliphatic carboxylic acid having 12 carbon atoms and an unsaturated aliphatic alcohol having 2 to 12 carbon atoms, an aromatic carboxylic acid having 7 to 12 carbon atoms and an ester formed from a saturated or unsaturated aliphatic alcohol having 1 to 12 carbon atoms or a ketone having 3 to 13 carbon atoms.

The resulting magnesium dihalide donor adduct is then reacted with a Si or Sn compound and a titanium or vanadium compound. This reaction can be carried out according to several different embodiments.

Preferred embodiments include, for example, 1) a method in which a magnesium dihalide donor adduct is contacted with a silicon and / or tin halide compound and then contacted with a transition metal compound, and 2) a method in which a magnesium dihalide donor adduct is contacted substantially simultaneously with a silicon and / or tin halide compound. After a portion of the magnesium dihalide donor adduct has been treated according to Method 1), the remainder is treated according to Method 2) and the resulting mixture is used as the transition metal catalyst component a), or when one of the silicon and / or tin halide compounds and the transition metal compound are used in excess of feed. and termination must occur simultaneously. Thus, the carrier-producing reaction can sometimes be carried out partially separately from the rest of the reaction.

The reaction of the magnesium dihalide donor adduct with a Si or Sn compound and a titanium or vanadium compound can be carried out in the presence or absence of an organic solvent. In this case, it is not necessary to separate the adduct from the reaction product system, but a Si or Sn compound and a Ti or V compound may preferably be added to the reaction product system containing the adduct. Using the method described above, 1) the magnesium dihalide donor adduct is contacted with a Si and / or Sn compound at a temperature of -20 to 100 ° C, preferably 20 to 1 ° C, and upon contact with the transition metal compound, the temperature is -20 to 1 ° C. , preferably 20-110 ° C. When using method a), the reaction temperature is -20 to 10 ° C, preferably 20 to 0 ° C.

7 57601

The reaction time is about 10 minutes to 5 hours. Usually the Si or Sn compound is used in an amount of at least 1/50 times the molar amount of the donor, preferably at least (molar amount) 1/1 + times the molar amount of the donor used. It is not necessary to use it in large amounts, but usually sufficient amounts are 1/50 to 50 times the molar amount of donor used. If the amount is too small, the particle size distribution of the obtained polymer tends to be uneven. In addition, there is a tendency for the formation of coarse particles unsuitable for continuous polymerization. Furthermore, there is a tendency to form only a catalyst with low polymerization activity. Preferably, amounts in excess of the above lower limit are used.

When reacting a magnesium dihalide donor adduct with a Si or Sn compound and a titanium or vanadium compound, conventional mixing equipment or mechanical grinding equipment such as a ball mill can be used, if desired.

At the end of the reaction, a product is formed which is insoluble in the hydrocarbon. The product can be separated from the hydrocarbon soluble material by methods such as filtration, decantation and other suitable means for solid-liquid separation. It is preferable to wash the product with an inert organic solvent such as hexane, heptane or petroleum. The catalyst component a) thus obtained can be used as it is without subjecting it to a special heat treatment.

The Si or Sn compound is a halogen compound of Si, a halogen compound of Sn, an organohalogen compound of Si, and an organohalogen compound of Sn having the formula

M + R1R2R3R1

wherein M is Si or Sn, R 1, R 2, R 2 and are the same or different, hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy, phenyl, phenoxy of 1 to 8 carbon atoms or halogen, wherein at least one of said substituents is a halogen atom.

The titanium and vanadium compound is a compound of the formula TiX 2; Ti (0R), ^ _ n X n; VOX1 or VX1, wherein X is halogen, R is an alkyl group having 1 to 12 carbon atoms, and n is a positive number zero or less than i +. Titanium compounds are more popular, and in particular compounds of the formula TiX 2, especially titanium tetrachloride. According to the present invention, a catalyst composition is used which is a combination of the transition metal catalyst component a) described above and the organometallic catalyst component b) of the Group I-III periodic table.

β 57601

The organometallic compound catalyst component b) may be, for example, a compound of formula RM wherein R is an alkyl or aryl group and M is lithium, sodium or potassium, a compound of formula R 1 M * wherein E is as defined above and M 'is zinc or cadmium, a compound of formula Ε ^ _ ^ ΜβΧ ^ wherein R is as defined above, X is a halogen atom and 1 is zero or 1f is a compound of formula MAIR ^ wherein R and M are as defined above, R 'A1X wherein R 'is a hydrogen atom or an alkyl or aryl group, X is as defined above and m is zero or a positive number not greater than 3, a compound of formula R' Al (OR) wherein in the formula R 'is as defined above for 3 — nn _ and n is a positive number greater than 0, but

not greater than 3, and a compound of formula RA1 (OR) X, wherein R and X

are as defined above.

If two or more of the symbols R, R 'and X are in any of the above formulas, these may be the same or different. Symbols R and R *

The alkyl groups represented by R 1 preferably contain 1 to 12 carbon atoms and the symbols R

and the aryl groups represented by R 'are preferably phenyl and benzyl groups. X is preferably chlorine or bromine. Examples of the above-mentioned organometallic compounds corresponding to the formulas R 'A1X, R * Al (OR), R., MgX, are trialkyl-3-mm 3-nn 2-1 ^ 1' aluminum compounds, alkylaluminum halides, alkylaluminum hydrides, dialkyl-zinc compounds, dialkylmagnesium compounds and alkylmagnesium halides. Specific examples include triethyl aluminum, dietyylialuminiumhydridi, tri-propyylialuminium, tributyylialuminium, diethylaluminium chloride, Diethylaluminum bromide, dietyylialuminiumetoksidi, dietyylialuminiumfenoksidi, etyylialuminium-etoksikloridi and ethylaluminium sesquichloride, these are the most popular of trialkyl aluminum, such as triethyl aluminum and tributyylialuminium, dialkyylialuminium-hydrides, such as di-isobutyl aluminum hydride, and dialkylaluminum halides such as diethylaluminum chloride.

The polymerization of olefins using the catalyst of this invention is preferably carried out in an inert organic liquid medium (or an inert organic solvent). The amount of the transition metal catalyst component a) is preferably 0.001 to 0.5 mmol, calculated as titanium or vanadium atoms per liter of inert organic liquid medium. The amount of the organometallic compound catalyst component b) formed by the metal of groups I-III of the Periodic Table is suitably at least 0.01 mol, preferably 0.01 to 50 mmol / l of an inert organic liquid medium.

9,57601

The polymerization reaction of olefins using the complex catalyst of the present invention can be carried out in the same manner as the polymerization of olefins using conventional Ziegler-type catalysts. The reaction is carried out with oxygen and hydrogen substantially excluded. A suitable inert organic liquid medium is used, for example an aliphatic hydrocarbon such as hexane or kerosene, and the olefin and catalyst and, if desired, another olefin and / or diolefin are fed to the medium in which the polymerization is carried out.

The polymerization temperature is usually 20 to 200 ° C, preferably 50 to 180 ° C.

2 2

The reaction can generally be carried out at a pressure of 1 to 50 kp / cm, preferably 2 to 20 kp / cm. The reaction is preferably carried out under elevated pressure. The control of the molecular weight distribution when using the catalyst composition of the present invention and hydrogen simultaneously takes place efficiently not only in a batch process but also in the continuous polymerization of olefins.

One advantage of using the catalyst system of this invention is that the polymer yield per unit weight of the transition metal is increased, the polymer yield per unit weight of the support is significantly increased, and the resulting polymer has a significantly high bulk density. In addition, the polymer obtained is not in the form of large coarse particles, but its particles have a very uniform diameter. As a result, the removal and transfer of the polymer becomes easy in a continuous process, and large amounts of polymer per unit weight of catalyst used can be easily produced by continuous polymerization. In addition, since the amounts of transition metal and halogen and the residual amounts of the carrier compound contained in the obtained polymer are very small, the degeneration of the articles made of polyolefin does not take place without special removal of these materials, and the products are well suited for conventional uses. The magnesium halides used in the present invention have the advantage that they are soluble in water and alcohols. Where it is necessary to completely remove the residues of the catalyst component, for example in the production of thin yarns or films, the addition of alcohol and / or water makes it easy to completely remove the catalyst components, including the support compound, In addition, it is very characteristic that no transition metal is present. . In catalyst systems without a support, small residual amounts of the transition metal compound cannot be avoided even when the residual catalyst is subjected to a decomposition treatment.

The carrier may contain small amounts of other metals such as calcium, aluminum, zinc, manganese, iron, nickel and cobalt.

.0 57601

The following examples illustrate this invention. In these examples, the reaction system was protected from oxygen and moisture from the beginning to the end of the polymerization.

Examples 1-7 and Comparative Example 1

Catalyst preparation

191 g of commercial anhydrous magnesium halide was suspended in 2 liters of purified petroleum, and each of the alcohols listed in Table 1 was added dropwise to the suspension at 50 ° C. After the addition, the mixture was stirred for 1+ hours.

A mixture of 6 moles of each of the transition metal compounds listed in Table 1 and 500 cm 2 of each of the silicon and / or tin halides listed in Table 1 was then added to the above suspension as a donor and the reaction was carried out at 80 ° C for 1 hour. The reaction product was washed thoroughly with neat petroleum support. to obtain the existing catalyst component. ~

Catalyst preparation B

191 g of anhydrous magnesium dihalide were suspended in 2 liters of pure petroleum and each of the alcohols listed in Table 1 was added to the suspension at 40 ° C as a donor. The mixture was stirred for h hours.

Two dropping funnels were used and 7 moles of each of the transition metal compounds listed in Table 1 and the amount of each of the silicon or tin compounds listed in Table 1 were charged to the other. These compounds were added dropwise at about the same time to the suspension and the mixture was reacted at 80 ° C for 3 hours. The reaction product was washed with petroleum to obtain a supported catalyst component.

Polymerization A 2-liter autoclave was charged with 1 liter of kerosene, 1 mmol of each organoaluminum compound listed in Table 2, and 0.007 mmol, calculated as titanium or vanadium metal, of each of the catalysts in A or B above, and the mixture was heated to 80 ° C. After adding hydrogen to a pressure value of U kp / cm, ethylene was continuously fed so that the total pressure of the autoclave reached 8 kp / cm, and the polymerization was carried out for 2 hours.

The polymer was filtered off and dried without removing the catalyst. The polymerization conditions and results for the preparation of the supported component as well as the preparation of the final component are shown in Table 2.

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Example 8 and Comparative Example 2

An autoclave with an effective capacity of 2 liters was continuously fed 1 liter per hour of hexane, 1 mmol per hour of triethylaluminum and each supported catalyst component prepared according to Example 1 and Comparative Example 1 (0.007 mmol calculated as titanium) and ethylene at a rate of 300 g per hour. At the same time, hydrogen was fed to the autoclave so that the melt index of the obtained polyethylene remained at 0.2 to 0.5, and the operation was maintained continuously for 180 hours. Approximately 300 g of polyethylene was formed per hour and the work was easy and there were no disturbances of any kind. However, when using the catalyst of Comparative Example 1, the precipitation of the polymer failed after 10 hours from the start of the polymerization due to the formation of a large amount of polymer with particles approximately the size of a rice grinder.

--- Example 9 0.01 mmol, calculated as titanium, of the supported catalyst component of Example 1 and 3 mmol of triethylaluminum were placed in 1 liter of fuel oil and hydrogen was introduced at a pressure of 3 kp / cm. A gaseous mixture of ethylene and propylene containing 1.5 mol% of propylene was then introduced into the mixture at a temperature of 80 ° C and the polymerization was carried out for 2 hours while maintaining the total pressure at 7 kp / cm. The amount of ethylene / propylene copolymer obtained was 311 g and the copolymer had a melt index of 1.8 and contained 3 methyl groups per 1,000 carbon atoms.

Examples 10 and 11 and Comparative Examples 2 and 3

MgCl 2 · 5011 ^ 0000 ^ 11 ^ and MgCl 2 · SCH 2 COCl 2 H 2 O were prepared synthetically and both were suspended in 2 moles of one liter of ethanol. To the suspension were added 5 moles of titanium tetrachloride and 20 moles of silicon tetrachloride, and the mixture was stirred at 120 ° C for 1 hour. After the reaction, the solid portion was washed to form a supported catalyst. For comparison, the above procedure was repeated, except that silicon tetrachloride was not used to form the supported catalyst component.

Polymerization

The polymerization was carried out under conditions similar to those described in Example 1, except that the amount of titanium metal in the supported catalyst component was changed to 0.01 mmol / l of ethanol. The results are shown in Table 3.

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Example 12 .... . 3 2 g of anhydrous magnesium chloride were dissolved in 20 cm of ethanol. 200 cm of kerosene, k cm of titanium tetrachloride and 30 cm of silicon tetrachloride were placed in a 1 liter flask. While stirring, an ethanolic solution of magnesium chloride was added dropwise. ..... _ o ......

After the addition, the mixture was stirred for 1 hour at 100 ° C to precipitate the resulting solid. The supernatant was washed thoroughly with hexane. It was found that 81 mg of titanium per gram of support catalyst component. Ethylene was polymerized under the conditions of Example 1 using this catalyst at a concentration of 0.007 mmol, calculated as the titanium atom, and 1 mmol of triethylaluminum. 39 g of polyethylene having a melt index of 5> 12 and a bulk density of 0.330 g / cm were obtained. This amount corresponds to 56300 g / Ti per mol and 9 to 900 g / g of the support catalyst component. The particle size distribution of the polymer was such that it contained 3.1 wt. - $ S particles larger than 1 * 2 mesh, ^ 16.6% particles 1 + 2-60 mesh, 38.1+% particles 60-100 mesh, 31.7% particles 100-150 mesh and 10, 2% particles finer than 150 mesh.

Example 13 0.01 mmol of the catalyst prepared according to Example 1 and 1 mmol of triethylaluminum were placed in 1 liter of petroleum and at 80 ° C, ethylene containing 10 volumes of tert-butadiene was added at a rate of 200 g / h. After one hour 3, 18 g of polyethylene having a density of 0.930 g / cm 3 and no more than 1 methyl group, 5.9 transvinyl groups and 0.3 vinyl groups per 1,000 carbon atoms were obtained.

Examples 11 + -23 and Comparative Examples 1+ and 5

Catalyst preparation

The anhydrous magnesium dihalides listed in Table 1+ were suspended in each 200 g of 2 liters of petroleum, and the electron donors listed in Table k were added dropwise to the mixture over 1 hour at room temperature. After the addition, the mixture was stirred for 1 hour and then each silicon or tin halide was added dropwise over 1 hour. Then, 15 moles of each transition metal compound was added, and the mixture was heated at 90 ° C for 1 hour with stirring. The reaction product was washed thoroughly with purified petroleum to remove excess titanium or vanadium halide.

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An autoclave with an effective capacity of 2 liters was continuously fed 1 liter per hour of hexane, 1 mmol / h of triethylaluminum and supported catalysts prepared as described in Examples 1H and 21 and Comparative Examples 1+ and 5 (0.007 mmol based on titanium content) and 300 g of ethylene were fed . At the same time, hydrogen was fed to maintain the melt index of the obtained polyethylene at 0.2-0.5, and the operation was continued for 180 hours. The results are shown in Table 6. In Examples 25 and 26, the method worked flexibly. However, in Comparative Example 6 (using a support-supported catalyst prepared according to Example 1+), polymer drop-off failed 10 hours after the start of polymerization because a large amount of polymer was the size of rice grit and the operation had to be stopped. Further, in Comparative Example 7 (using the supported catalyst component of Comparative Example 5), the polymer failed 3 hours after the start of the polymerization. The polymer also melted because it was not possible to remove the heat of polymerization, and it was impossible to continue the operation.

Table 6

Experiment Carrier- Average 180 hours after polymerization of the initial catalyst polymer Particle size component yield distribution, mesh g / h <1 * 2 1 * 2-60 60-100 100-150 150-200> 200

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Example 25 0.011 * mmol, calculated as titanium, of a support or catalyst component prepared according to Example II * and 3 mmol of triethylaluminum were placed in 1 liter of petroleum and hydrogen was fed at a pressure of 3 kp / cm. A gaseous mixture of ethylene and propylene with a propylene content of 1.5 mol was fed at 80 ° C and the polymerization was carried out for 2 hours at a total pressure of 7 kp / cm. 295 g of ethylene / propylene copolymer were obtained, the copolymer had a melt index of 1.2 and contained 3 methyl groups per 1,000 carbon atoms.

19 57601

Example 26 1 liter of petroleum was placed in a 2 liter flask and 0.2 mmol, calculated as titanium, of the support catalyst component prepared according to Example 19 and 2 mmol of triethylaluminum were added. The mixture was heated to 70 ° C. Propylene was fed at atmospheric pressure until the absorption of propylene was complete and then polymerization was performed for 1 hour. 139 g of polypropylene were obtained with a residual boiling heptane extract of U6%.

Examples 27 ~ 29

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1 hour. The reaction product was washed thoroughly with hexane and the excess titanium compound was removed.

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Polymerization A 2 liter autoclave was charged with 1 liter of petroleum, 1 mmol of an alkylaluminum compound and 0.007 mmol, calculated as titanium or vanadium, of a supported catalyst and the mixture was heated to 80 ° C. Hydrogen was added at a pressure of 1+ kp / cm and then ethylene was fed continuously so that the total pressure rose to 8 kp / cm and the polymerization was carried out for 2 hours. The polymer was filtered off and dried without removing the catalyst. Data on the preparation of the base-supported catalyst and the component obtained are shown in Table 8, as well as the polymerization conditions and the results obtained in Table 9.

Table 8

Experiment MgX ^ Electron donor Si or Sn compound Transition metal compound _Type Quantity x Type Quantity xx Type_Ti, V_X1

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8 "EtOH 6 - 0 TiCl 2 + 1 683 9" MeCO 2 E 6 6 TiBr 2 32 715 x, xx: mol / mmol Mg

Ti, V: atomic number of transition metal, mg / g, per gram of catalyst supported by the support X ': atomic number of halogen, mg / g, per gram of catalyst component supported by the support

Me: methyl group, Et: ethyl group, Hex: hexyl group, Bu: butyl group, X: halogen.

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Comparative Example 10

One mole of anhydrous magnesium dichloride was suspended in one liter of petroleum, and 6 moles of ethanol was added to the suspension. The mixture was stirred at ij-0 ° C for 1 hour. Then 2.5 moles of diethylaluminum chloride were added followed by 1.5 moles of TiCl 2. The reaction was carried out at 120 ° C for 1 hour. When the solid was separated and analyzed, it was found that there were 65 mg of Ti atoms per gram of solid.

The catalyst thus prepared was added to one liter of petroleum 0.01 mmol, calculated as titanium, and an additional 2 mmol of CH 2 SiHCl 2 was added. Ethylene was polymerized in this system for 2 hours at 80 ° C while introducing hydrogen at 2 ° C / cm 2 / cm. The partial pressure of ethylene was 4 kp / cm. No polymer was formed.

0 *

Claims (5)

1. Methods to homopolymerize or copolymerize ethylene, propylene, a mixture of ethylene or another o-olefin, a mixture of ethylene or propylene and a diolefin or a mixture of ethylene, another ci-olefin and diolefin in the presence of a catalyst consisting of a) a catalyst component of a transition metal prepared by reaction of a titanium or vanadium compound with a solid support of a magnesium compound, and b) a catalyst component of a metal-organic compound of a metal belonging to Group I-III of the Periodic Table the system, characterized in that the transition metal component is prepared by reacting with each other (i) a solid support which is an addition compound obtained from a magnesium dihalide and an electron donor which is water; a saturated or unsaturated aliphatic alcohol having 1 to 12 carbon atoms; a saturated or unsaturated aliphatic carboxylic acid having 1 to 12 carbon atoms; an ester formed from a saturated aliphatic carboxylic acid of 1-12 carbon atoms and a saturated aliphatic alcohol of 1-12 carbon atoms; an ester formed from a saturated aliphatic carboxylic acid of 1-12 carbon atoms and an unsaturated aliphatic alcohol of 2-12 carbon atoms; an ester formed from an unsaturated aliphatic carboxylic acid of 3-12 carbon atoms and a saturated aliphatic alcohol of 1-12 carbon atoms; an ester formed from an unsaturated aliphatic carboxylic acid of 3-12 carbon atoms and an unsaturated aliphatic alcohol of 2-12 carbon atoms; an ester formed from an aromatic carboxylic acid of 7 to 12 carbon atoms and a saturated or unsaturated aliphatic alcohol of 1 to 12 carbon atoms; or an aliphatic ketone having 3 to 13 carbon atoms, (ii) a Si or Sn compound of the formula R, R_R R, M 1 2 3 3 wherein M is Si or Sn and R 2, R 2, R 2 and R 2 which may be the same or different, denotes a hydrogen atom, an alkyl group having 1-carbon atoms, a phenyl group, an alkoxy group of 1-8 carbon atoms, a phenoxy group or a halogen atom, wherein at least one of said substituents is a halogen atom and (iii) a titanium or vanadium compound of the formula TiX; Ti (OR), X; VOX, or VX, 4 '4-nn 34 in which Formulas X is a halogen atom, R is an alkyl group of 1-12 carbon atoms and n is noil or a positive tai less than U, and that the mole amount of Si or Sn The compound is at least 1/50 times the mole amount of the electron donor, 28 57601 2. A method according to claim 1, characterized in that the homopolymerization or copolymerization is carried out in an inert, organic liquid medium. 3. A process according to claim 2, characterized in that the amount of the transition metal is 0.001-0.5 mmol calculated in transition metal atoms per liter of inert organic solvent, and the amount of the metal organic catalyst component is 0.01-50 mmol calculated in metal atoms per liter. inert organic solvent. A method according to claim 1, characterized in that the magnesium dihalide is constituted by magnesium dichloride or magnesium dibromide. A catalyst used in the process according to any one of claims 1-U and comprising a) a catalyst component of a transition metal prepared by reaction of a titanium or vanadium compound with a solid support of a magnesium compound, and b) a catalyst component of a metal-organic compound of a metal belonging to groups I-III of the periodic system, characterized in that the transition metal component is prepared by reacting with each other (i) a solid support which is an addition compound obtained from a magnesium dihalide and an electron donor which is water; a saturated or unsaturated aliphatic alcohol having 1 to 12 carbon atoms; a saturated or unsaturated aliphatic carboxylic acid having 1 to 12 carbon atoms; an ester formed from a saturated aliphatic carboxylic acid of 1-12 carbon atoms and a saturated aliphatic alcohol of 1-12 carbon atoms; an ester formed from a saturated aliphatic carboxylic acid of 1-12 carbon atoms and an unsaturated aliphatic alcohol of 1-12 carbon atoms; an ester formed from an unsaturated aliphatic carboxylic acid of 3-12 carbon atoms and a saturated aliphatic alcohol of 1-12 carbon atoms; an ester formed from an unsaturated aliphatic carboxylic acid of 3-12 carbon atoms and an unsaturated aliphatic alcohol of 2-12 carbon atoms; an ester formed from an aromatic carboxylic acid of 7 to 12 carbon atoms and a saturated or unsaturated aliphatic alcohol of 1 to 12 carbon atoms; or an aliphatic ketone having from 3 to 13 carbon atoms, (ii) a Si or Sn compound of the formula Y2R3RUM wherein M is Si or Sn and, R2, R an alkyl group of 1-8 carbon atoms, a phenyl group, an alkoxy group of 1-8 carbon atoms, a phenoxy group or a halogen atom, wherein at least one of said substituents is a halogen atom and