FI57264B - SAETT ATT HOMOPOLYMERISERA ELLER COPOLYMERISERA ETHYL PROPYLEN ELLER ETHLEN OCH ALPHA-OLEFIN OCH / ELLER EN DIOLEFIN SAMT EN CATALYST COMPOSITION FOR ANALYZING VID SAETTET - Google Patents

Description

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Patent- och registerstyrelsen '' Aniöiun uti ** d och uti.ikrift «i pubiicand 31.03.80 (32) (33) (31) Requested front» —Begird priority 1 ^ 4.09.72 20.03.73 Japan-Japan (JP) 91807/72, 31382/73 Proven-Styrkt (71) Mitsui Petrochemical Industries, Ltd., 2-5 »3-chome, Kasumigaseki,, Chiyoda-ku, Tokyo, Japan-Japan (JP) (72) Norio Kashiwa, Yamaguchi -Ken, Saburo Fuji, Hiroshima-ken, Masanide Tanaka, Yamaguchi-ken, Japan-Japan (JP) (71 *) Oy Kolster Ab (5M Method of homopolymerizing or copolymerizing ethylene, propylene or a mixture of ethylene and otolefin and / or diolefin as well as the catalyst composition used in the process - Sätt att homopolymerisera eller copolymerisera ethyl, propylene or ethylene och # -olefin och / eller en diolefin samt en catalyst catalyst composition for setting the conditions

The invention relates to a process for homopolymerizing or copolymerizing ethylene, propylene or a mixture of ethylene and β-olefin and / or diolefin such as butadiene, ethylidene norbornene or dicyclopentadiene in a manner which has a commercial advantage and high quality reproducibility, using a new catalyst composition, to give the polymer a suitable particle size and narrow particle size distribution and allows easy control of the melt index of the obtained polymer.

Previously, GB Patent 1,256,851 proposed the use of a solid reaction product as a transition metal catalyst which was capable of imparting a broad molecular weight distribution to a polyolefin and which was obtained by carrying a solid 2-valent metal, e.g. partially hydroxylated halide dioxide, complex oxide, complex hydroxide, alcoholate, inorganic oxyacid salt or mono- or polycarboxylic acid salt, to react with the organoaluminum compound or organomagnesium compound without diluting with the solid end product was removed from this reaction product system. In this patent, it is essential to separate the solid reaction product from the product obtained from the reaction of the support with the organometallic compound. It is further required that the separated solid reaction product is washed as an inert solvent and then dried, and the reaction of this product with the transition metal compound is carried out without a trace of a diluent. As a result, the method of preparing the catalyst component has the disadvantage that the finely divided solid is separated and washed without contact with air or moisture and then completely dried.

Prior to the attempt described above, GB 927 969 proposed the preparation of polyolefin, in particular polypropylene with excellent stereospecificity, by vapor phase polymerization using as a catalyst component a reaction product obtained by reacting organometride with sodium chloride or sodium carbonate as a and then reacting the obtained reaction product with a transition metal compound. In this proposal, the above-mentioned catalyst component is essentially heat-treated, and if this heat treatment is not performed, the obtained catalyst component cannot produce polymers with increased stereospecificity. In addition, the catalyst obtained in this proposal has very low activity.

Studies have now been carried out on improved catalysts which are well suited for the polymerization or copolymerization of olefins and it has been found that catalysts with improved high activity are capable of producing polymers of suitable particle size, narrow particle size distribution and easy control of the melt index of the obtained polymer. the above-mentioned complex and careful control or heat treatment of the catalyst component in the above-mentioned previously known proposals. It has been found that this improvement can be accomplished by using an alcohol adduct of magnesium halide as a solid carrier.

Accordingly, it is an object of the present invention to provide an improved process for polymerizing or copolymerizing an olefin.

It is another object of this invention to provide a catalyst composition for use in the above process.

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

According to the complicated process of this invention, an olefin or olefin is polymerized and another olefin and / or diolefin is copolymerized in the presence of a catalyst consisting of (a) a transition metal catalyst component obtained by reacting a solid support of a magnesium halide alcohol adduct with an organometallic metal group III group and then reacting the reaction product with a titanium or vanadium compound and (b) an organometallic compound of a metal of Groups I-III of the Periodic Table.

This invention is particularly effective for ethylene and propylene, especially for the polymerization of ethylene and the copolymerization of ethylene with i-olefin and / or diolefin.

The process of this invention makes it possible to obtain polymers suitable for the desired uses, ranging from those having a broad molecular weight distribution suitable for blow molding to those having a narrow molecular weight distribution. In addition, the method of the present invention provides the following advantages.

(a) Since the yield of the polymer per unit amount of transition metal atom and the number of units per solid catalyst component is very high, it is completely unnecessary to remove the catalyst residue from the obtained polymer.

(b) With high reproducibility, polymers with a suitable particle size and narrow particle size distribution and high bulk density can be obtained, and hardly any polymer formation occurs in the form of coarse or ultrafine particles. This makes it possible to continue the polymerization process continuously for a considerably longer time.

(c) Since the molecular weight of the polymer can be effectively controlled even when the partial pressure of the hydrogen used as a chain transfer agent is low, it is easy to obtain a polyethylene wax which is a low molecular weight polymer or relatively low molecular weight polymers for high speed injection molding.

(d) Copolymerization of ethylene, especially with a diolefin such as butadiene, can be carried out with very high catalyst activity and polymers with large amounts of double bonds in the molecules can be easily produced. These highly unsaturated polymers are valuable because they can be easily modified by a grafting reaction or a high molecular weight reaction.

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It (e) The solid catalyst component can be easily prepared.

When conventional catalysts have one or more of these advantages separately, it is to be understood that the catalyst composition of this invention has all of these advantages together.

Due to the advantage of catalytic activity (a), the amount of catalyst can be greatly reduced. Thus, the resulting polymer contains a significantly reduced amount of titanium or halogen, which could cause poor color of the polymer or clogging or corrosion of the casting machine. The removal of the catalyst from the polymer can be bypassed without much concern and this can lead to a significant reduction in production cost.

Advantage (b) results from the fact that the catalyst of the present invention can be used to prepare polymers having a high bulk density and a uniform particle size distribution. In conventional methods, the polymer tends to adhere to the wall of the polymerization vessel and the coarse particles of the resulting polymer are sedimented into the polymer removal tube of the polymerization vessel, which easily causes difficulty in removing the polymer slurry. This has been the greatest difficulty with continuous polymerization. In the case of such a situation, undesired accidents may occur, such as failure of uniform mixing in the polymerization vessel or melting of the polymer due to heat rise, and eventually it is necessary to interrupt the polymerization. The process of the present invention can overcome such difficulty.

Due to advantage (c), the present invention makes it possible to easily produce polymers with the desired low molecular weight using a very small amount of hydrogen (low partial pressure) and a small amount of catalyst. The catalyst of the present invention has the property that hydrogen can be efficiently added to the polymer and, in addition, the molecular weight of the polymer can be easily controlled over a wide range according to the partial pressure of hydrogen. Using conventional catalysts, the partial pressure of hydrogen must be significantly increased if polymers with a sufficiently low molecular weight are to be obtained and in order to overcome the consequent reduction in polymerization activity, the only way is to increase the amount of catalyst. In addition, the molecular weight can only be adjusted with hydrogen within narrow limits.

One example of advantage (d) is that a highly unsaturated polyethylene containing a large amount of diolefin, such as butadiene, can be prepared in good yield using the catalyst of this invention. For example, polyethylene containing about 20 double bonds per 1,000 carbon atoms can be easily obtained. Many of the conventional Ziegler-type catalysts do not show high activity in a system in which the diolefin is present and the diolefin can be incorporated into the copolymer only to a small extent.

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As an advantage (e), the process for preparing the catalyst can be considerably simplified compared to the prior art. In previously known companies, operations such as separation, washing and drying of the finely divided compound have been essential in the preparation of the catalyst. Because these operations are performed with a finely divided compound, they require a very long time and due to the need for these operations, a large loss of the final product occurs. Furthermore, in conventional methods, the amount of the transition metal compound used to prepare the catalyst but not attached to the support is very large compared to the amount of the compound attached to the support and used as a catalyst. Such a transition metal compound should be removed as much as possible, for example by washing. The excess transition metal compound used contains by-products formed during the preparation of the catalyst and also contains the inert solvent used for washing. Thus, the separation and re-purification of this compound requires a lot of time and cost.

On the other hand, in the preparation of the catalyst of the present invention, the separation of the reaction product, washing, drying, and so on, are not essential during the preparation of the catalyst. This greatly simplifies operation and equipment and greatly reduces the time required to prepare the catalyst. It is possible to avoid complex and costly operations such as discarding or regenerating by-products.

The solid carrier used in the present invention is a carrier in which the alcohol is coordinated with a magnesium dihalide, preferably magnesium dichloride. The properties of the obtained catalyst may vary somewhat depending on the type and amount of alcohol. It is generally recommended that the amount of alcohol to be added be 0.1 to 10 moles per mole of magnesium dihalide. To prepare the titanium catalyst component, which component forms a catalyst system with high activity and which allows the treatment of the catalyst residue after polymerization to be avoided, preferably at least U moles of alcohol are used, most preferably at least 6 moles per mole of magnesium dihalide.

Magnesium dihalide in anhydrous form is usually used. The term "anhydrous" as used herein does not preclude the use of compounds of reagent purity, commercially available as "anhydrous", which contain very small amounts of moisture.

If the amount of alcohol is too small, the polymerization activity of the catalyst per unit number of titanium or vanadium atoms is low, and the obtained catalyst produces polymers in the form of coarse or ultrafine particles which do not have a uniform particle size distribution of 6,576,264. Pretreatment with alcohols results in a finer distribution of magnesium dihalide particles than before treatment, and infrared absorption spectroscopic analysis and X-ray analysis of the product show that it has been converted to an adduct of magnesium dihalide and alcohol. The reaction of the magnesium halide support with the alcohol is generally carried out at temperatures of -10 to + 200 ° C. The reaction proceeds satisfactorily at room temperature. In most cases, the reaction temperature is 0 to 100 ° C, preferably 10 to 60 ° C. The reaction time is usually 10 minutes to 2 hours. The reaction is preferably carried out in the absence of water and molecular oxygen. It is usually carried out under a nitrogen atmosphere in an inert organic medium. Examples of the medium may be those used in the polymerization and include hexane, heptane, kerosene, benzene, xylene and fluorobenzene.

The alcohol-added magnesium dihalide is prepared by conventional methods. For example, it can be prepared by reacting metallic magnesium with ethanol containing dry hydrochloric acid to form MgCl 2 .EtOH (Russian Journal of Inorganic Chemistry Vol. 12, No. 6, 901 (1967)).

The resulting alcohol adduct of magnesium dihalide is then reacted with a metal organometallic compound of Groups I-III of the Periodic Table.

In this case, it is not necessary to separate the adduct, but the organometallic compound can advantageously be added to the reaction product system containing the adduct. The reaction is preferably carried out in the absence of water and molecular oxygen, as above. The reaction temperature is, for example, between -20 and 100 ° C, preferably between 20 and 10 ° C. The reaction time is about 10 minutes to about 4 hours. Usually, at least 0.1 mole of the organometallic compound per mole of alcohol adduct of magnesium is used. It is not necessary to use it in large quantities, but usually 0.5 to 10 moles are sufficient. In particular, when it is desired to prepare a catalyst having a high activity and suitable for continuous polymerization over long periods of time, the organometallic compound is used in an amount such that the amount of organic groups of the organometallic compound is 0.1 to 1.5 moles, preferably 0.5 to 1 mole / magnesium dihalide. the alcohol adduct per mole of the hydroxy group of the alcohol.

If the amount of organic groups of the organometallic compound is small compared to the amount of hydroxy groups of the alcohol when the alcohol adduct of magnesium dihalide is reacted with the organometallic compound, the catalyst was not suitable for continuous slurry polymerization over long periods of time. Therefore, it is preferable that the number of organic groups be selected experimentally in the above range depending on the type of alcohol to be added and the organometallic compound to be reacted with the adduct. structure, which crystals are neither magnesium dihalide nor alcohol adduct crystals.

The reaction product of the alcohol adduct of magnesium dihalide and the metal organometallic compound of Groups I-III of the Periodic Table can be directly reacted with a titanium or vanadium compound to form a transition metal catalyst component (a), although it is possible to separate an integral part of the reaction product the titanium or vanadium compound is about 1: 0.1-10 and commercially preferably 1: 0.1-5. In general, this reaction is carried out at temperatures between -50 and + 250 ° C for a period of 10 minutes to 5 hours.

The reaction proceeds satisfactorily even at room temperature, but can be carried out at an elevated temperature. Preferably, the reaction is carried out in the presence of an inert solvent such as a hydrocarbon or a halogenated hydrocarbon with conventional stirring or mechanical grinding using a ball mill. At the end of the reaction, a hydrocarbon-insoluble product is formed. The product can be separated from the hydrocarbon soluble material, for example, by filtration, decantation, or other suitable means of separating the solid and the liquid. In most cases, no. however, this delivery is required. The catalyst component (a) thus obtained can be used as it is without being subjected in particular to heat treatment.

Preferred examples of the alcohols used to produce the alcohol adduct of the magnesium dihalide carrier include 1- or 2-membered aliphatic and aromatic alcohols containing up to 12 carbon atoms, which may be used alone or in combination.

Specific examples of alcohols include saturated aliphatic alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol or octyl alcohol; unsaturated aliphatic alcohols such as allyl alcohol or undecyl alcohol; an aliphatic polyhydric alcohol such as ethylene glycol, glycerol or propylene glycol; carbitols such as butyl carbitol and aromatic alcohols such as benzyl alcohol,

The metal organometallic compound of the groups I-III of the Periodic Table used for the reaction with the alcohol adduct of the magnesium dihalide support is a compound of the formula RM, R M, R_MgX, MA1R. , R 'A1X, R' Al (OR) or 7 7 2 2-p ^ p h7 3-m m '3-nn RA1 (0R) X, in which R is an alkyl or aryl group, M is lithium, sodium or a potassium atom, X is a halogen atom, p is zero or 1, R 'is a hydrogen atom or an alkyl or aryl group, m is zero or a positive number greater than zero but not greater than 3.

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If each of the above formulas contains two or more of the groups R, R 'and X, they may be the same or different. Preferred alkyl groups denoted by R or R 1 contain 1 to 12 carbon atoms, and preferred aryl groups denoted by R or R 'are phenyl and benzyl groups. X is preferably chlorine or bromine. Of the above organometallic compounds, organoaluminum compounds are particularly preferred, especially those having the formula RJ_ A1X.

3 ~ m m

The titanium or vanadium compounds used according to the invention are compounds of the formula TiX 4, Ti (OR) 2 -nXn, VOX 4 or VX 2, in which X is a halogen atom, R is an alkyl group preferably containing 1 to 12 carbon atoms, and n is zero or a positive number less than U. Titanium compounds, and in particular TiX 4 compounds of the formula, especially titanium tetrachloride, are considered to be most preferred.

The present invention uses a catalyst consisting of a combination of the transition metal catalyst component described above and the organo-metallic compound component of groups I-III of the Periodic Table. The magnesium dihalide support is reacted with an alcohol to form an adduct, which is then reacted with a metal organometallic compound of Groups I-III of the Periodic Table. The reaction product is then reacted with a titanium or vanadium compound to form a transition metal catalyst component. The resulting transition metal catalyst component is further reacted with the catalyst component in the organometallic compound to form the catalyst of the present invention.

The organometallic compound catalyst component combined with the transition metal catalyst component may be the same, but not necessarily the same, as those used for the reaction with the alcohol adduct of magnesium dihalide.

For the organometallic compound, the catalyst component b) has the formula R ’A1X, R * A1 (OR), RA1 (OR) X or 3-m m 3 — n n

Rg ^ MgXp, in which R * is a hydrogen atom or an alkyl or aryl group, X is a halogen atom, m is zero or a positive number not greater than 3, n is a positive motion greater than zero but not greater than 3 and p is zero or 1, or a dialkylzinc compound. Examples are trialkylaluminum, alkylaluminum halides, alkylaluminum hydrides, dialkylzincs, dialkylmagnesium and alkylmagnesium halides. Specific examples include triethylaluminum, diethylaluminum hydride, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, diethylaluminum phenoxide, ethylaluminum ethoxychloride and ethylaluminum4. Of these, trialkylaluminum such as triethylaluminum or tributylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydrides such as diisobutylaluminum hydride and dialkylaluminum halides such as diethylaluminum chloride are preferred.

The polymerization using the catalyst of this invention is preferably carried out in an inert medium. The amount of the transition metal catalyst component is 0.001 to 100 millimoles per titanium atom per liter of inert liquid medium. The amount of the metal organometallic compound (b) of the groups I-III of the Periodic Table is 1 to 10,000 moles per mole of titanium or vanadium atom of the titanium or vanadium compound.

The polymerization reaction using the catalyst of the invention can be carried out in the same manner as the polymerization of the olefin using conventional Ziegler-type catalysts. The reaction is performed essentially without oxygen and water. A suitable inert organic liquid medium is used, for example an aliphatic hydrocarbon such as hexane, heptane or kerosene, and the olefin and catalyst and, if desired, another olefin and / or diolefin are fed to the medium and the polymerization is carried out.

When ethylene is polymerized using the catalyst of this invention in the presence of hydrogen, the presence of hydrogen at a low concentration contributes to the reduction in molecular weight and the molecular weight distribution can be effectively expanded. The partial pressure of hydrogen in the polymerization system can be varied between 1-99% of the total pressure if required. Hydrogen may be added at the initial stage of ethylene polymerization or ethylene and hydrogen may be added simultaneously. If desired, hydrogen can be fed to the reaction system intermittently. The polymerization temperature is 20-200 ° C.

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The reaction is carried out at a pressure of 1 to 100 kg / cm. Preferably, the reaction is carried out under elevated pressure. Controlling the molecular weight distribution by using together the catalyst composition of this invention and hydrogen is effective not only in a batch-type process but also in the continuous polymerization of ethylene. When polymerizing or copolymerizing ethylene with the catalyst system of this invention, the molecular weight of the polymer can be adjusted to some extent by varying the polymerization conditions, such as polymerization temperature or catalyst molar ratio, but adding hydrogen to the polymerization system is most effective. Even at low partial pressure of hydrogen, a reduction in molecular weight is sufficient. Furthermore, the molecular weight can be adjusted over a wide range and polymers with a molecular weight as low as several hundred to several thousand can be easily obtained with high catalyst efficiency. This is a very notable feature of the catalyst composition of this invention in that it is difficult to obtain polymers with such a low molecular weight with conventional catalyst systems.

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Examples of β-olefins or diolefins copolymerizable with ethylene include propylene, butene-1, hexene-1,1-methylpentene-1, octene-1, butadiene, isopropene, ethylidene norbornene, dicyclopentadiene and 1,1-hexene. An increase in polymer yield and polymer bulk density, etc., can be attempted by adding various additives used in the polymerization reaction catalyzed by conventional Ziegler-type catalysts, e.g. by adding polysiloxane or ester to the polymerization system.

The following examples illustrate the present invention in which the reaction system was protected from oxygen and moisture from the beginning to the end of the polymerization.

Example 1

Catalyst Preparation 953 grams (10 moles) of commercially available anhydrous magnesium dichloride was suspended in 10 liters of hexane, and 60 moles of ethyl alcohol was added dropwise at room temperature over 30 minutes. At the end of the addition, the solution was stirred for 30 minutes at room temperature. The product was identified by X-ray analysis and found to consist of MgCl 2 .6EtOH crystals. While keeping the temperature of the reaction system below 1 + 0 ° C, 31 moles of diethylaluminum chloride was added dropwise, and the mixture was stirred for 30 minutes to form a crystalline compound other than MgCl 2 and MgCl 2 .6EtOH. Then 5 moles of titanium tetrachloride were added and the mixture was stirred for 6 hours at 30 ° C. The resulting catalyst was ready for use in polymerization.

Polymerization (1) A 2-liter autoclave was charged with 1 liter of kerosene, 0.1+ millimoles of triethylaluminum, and 0.0025 millimoles, calculated as titanium metal, of the above-mentioned titanium catalyst. The reaction system was heated to 80 ° C. Hydrogen was fed to the autoclave at a partial pressure of up to 3 kg / cm and ethylene was fed continuously to maintain a total pressure of 7 kg / cm and polymerized for one hour.

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to give 156 g of polyethylene having a bulk density of 0.32 g / cm 3 and a melt index of 8.9.

The activity of the catalyst was 62 1 * 00 g polymer / millimole Ti x hour, which corresponded to 312,000 g polymer / g Ti x hour x ethylene atm. X-ray analysis showed that the polymer contained 0.5 ppm titanium and 7 ppm chlorine.

The particle size distribution of the polymer was as follows:

Particle size Greater than 1 + 2 1 + 2-60 60-100 100-150 150-200 Smaller (mesh) than 200

Distribution 1.8 12.0 51.2 23.2 8.9 2.9 (w / w) 11 57264 (2) A 2-liter autoclave was continuously charged hourly with 1 liter of hexane, 0.5 millimoles of triisobutylaluminum and 0 .0025 millimoles, calculated as a titanium atom, of the catalyst component prepared above and at a temperature of 80 ° C were fed to the system 300 g per hour of ethylene while adjusting hydrogen to obtain a melt index of 1 + -6. The polymerization was carried out continuously for two weeks. The operation was easily carried out to give 270-295 g of polymer per hour. At the end of the polymerization, the autoclave was examined, but no difficulties were observed, such as the formation of an agglomerated mass or films detrimental to continuous polymerization.

Example 2

In the preparation of the catalyst shown in Example 1, 2 moles of titanium tetrachloride were added instead of 5 moles of titanium tetrachloride to form the catalyst in the same manner.

A 1 liter autoclave was fed with 1 liter of kerosene, 1 mmol of triisobutylaluminum hydride and 0.001 mmol of catalyst, calculated as titanium atoms, and 150 grams / hour of ethylene at 160 ° C. Hydrogen was continuously introduced into the autoclave to obtain polyethylene having a viscosity average molecular weight of 3,000-3,600 to obtain 120 grams of polymer on average per hour. The total pressure of the polymer system was 30 kg / cm. The specific activity corresponding to polyethylene was 120,000 g / mmol Ti, h.

Example 3

The catalysts were prepared in the same manner as in Example 1, except varying the types of alcohol and alkylaluminum, and the polymerization of ethylene was performed in the same manner as in Example 1. The results are shown in Table 1. The table also includes the results of Comparative Examples 1-5. circuit.

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table 1

Test- Carrier Alcohol Organometallic Transition metal titanium numbers compound compound

Type Quantity Type Quantity Type Quantity Type Quantity (mol) (mol) (mol) (mol) 1 MgClg 10 C2H50H kO EtgAlCl 19 TiCl ^ 3.5 2 "10 CH-OH 50 Et. -A1C1. C 32" 2 3 1 »5 1» 5 3 "10 n-BuOH 50 Et 2 Al 17 TiBr ^ 1 U” 10 C 2 H 5 OH 60 EtgAl (OEt) 30 TiCl 2

Comparative Example 1 MgCl 2 10 EtgAlCl 19 TiCl 3 3.5 2 CaCO 3 10 - - "19" 3.5 3 Mg (0H) Cl 10 - - "19" 3.5 h Mg (O "3.5 MgCl 2 10 CgH 2 OH 60 -" 3.5

Test numbers Polyethylene yield Melt index Volume- Weight of continuous polymerization (g / g Ti.h, ethylene atm.) ,. suitability (g / cm3) 1 2 ^ 3 000 5.6 0.30 Works for a week without difficulty 2,210,000 6.1 0.31 as well as 3,193,000 5.7 0.30 as well as 1+ l8l 000 5.8 0, 31 as well

Comparative Example 1,320 0.25 0.18 Polymer removal and 2,760 0.15 0.10 transfer come 3 1,020 0.10 0.08 due to unreasonably low bulk density 1,560 0.21 0.15 by weight and 5 1 110 0.05 0.08 continuous polymerization fails within 6 hours.

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Example 1+ 1 mole of commercially available anhydrous magnesium dichloride was suspended in 1 liter of petroleum, and a predetermined amount of each of the alcohols shown in Table 2 was added to the suspension at 20 ° C. The mixture was stirred for 1 hour, and a predetermined amount of each of the organometallic compounds shown in Table 2 was added dropwise at 25 ° C, followed by stirring for 1 hour. Either a titanium or vanadium compound was added to the mixture, and the mixture was stirred for two hours at 80 ° C. After the reaction, the reaction product was washed several times with kerosene.

A 2-liter autoclave was charged with 1 liter of petroleum, 1 mmol of alkylaluminum, and 0.0025 mmol of the catalyst component of the transition metal prepared above, calculated as the transition metal atom, and the system was heated to 80 ° C. Hydrogen was fed to the autoclave at a pressure of 3 kg / cm 2. Ethylene was fed to give a total pressure of 7 kg / cm and the polymerization of ethylene was carried out for 0.5 hours.

The results obtained are shown in Table 2. The table also shows the results of Comparative Examples 6 to 10, which were performed under conditions outside the scope of the present invention.

Table 2

Experience the numbers 6 7 8

Carrier MgCl 2 1 mol MgCl 2 1 mol MgCl 2 1 mol

Alcohol C2H5OH C2H5 ° H C2E5 ° H

Amount mol 6 5 ^

Organome- Type Et 2 AlCl Cl 2 H 2 MgCl EtAl (OEt) Cl Amount mol 2.7 1+ ^ compound *

Titanium- Type TiCl 2 Ti (OEt) (31 ^ TiCl 2 or van- Quantity χ0.8 0.5 diim- ’compound

Amount of titanium or vanadium in the solid (mg / g) 1 + 8 55 5Ö

Chlorine content of the solid part mg / g 52l + 507 511

The organometallic compound iBu, Al Et ^ Al (0n-Bu) n ς Et ^ AlH

Specific activity (g polymer / g Ti (V) .h. 335 800 278 300 259 100 C "2 atm).

Melt index 5.86 1 +, 26 5> 55 3

Bulk density g / cm 0.3! + 0.32 0.30 ". greater than ÄSS ^ 0 »ash weight. 2.3 2.6 2.3 size distribution less than 3.8 2.9 3> 3,200 mesh weight)? 111 57264

Table 2 (continued)

Experiment with numbers 9 10 Comparative Example 6

Carrier MgCl 2 1 mol MgCl 2 1 mol MgO 1 mol

Alcohol ° 2H5OH H00H2CH2OH

Number of mol 6 3

Organome- Type (Et Al) SO, EtAlCl Et Al Cl Compound Mol mol 2.5 2.5 2.7

Type ^ TiCl.

Titanium Wci ^ Ti (On-Bu) Cl3 TiCl ^ Amount mol / 0.5 duni compound (0.2 0.5 0.5 Ϊ6

Amount of Ti 1 + 5 1 + 1 titanium or vanadium V 21 contained in the solid part in mg / g

Chlorine content of the solid mg / g 581 556

Organometallic compound Et 2 Al Et 3 A Et 3 A 1

Specific activity (g polymer / g Ti (V) h. C "2 atm) 108,000 129,600,590

Melt indexes 3.15 1 +, 51 0.11

Bulk density g / cm 2 0.31 0.31 0.12

Bigger than

Polymer 1 * 0 mesh weight # 1, 9 2.8 58.0 particles · ·, ·. . , Smaller than the size distribution of 200 mesh weight # 2.7 2.6 0.5

Experiment Numbers Comparative Example 7 Comparative Example 8 Comparative Example 9 *

Carrier MgCl 2 1 mol MgiO 1 Cl 2 H 2 g 1 mol Mg (OEt) 2 1 mol

Alcohol C2H5OH “” Amount mol 2 -

Organome- Type EtgAlCl EtgAlCl, Maola mol - 2.7 2.7 compound

Titanium- Type TiCl 2 TiCl 2 TiCl 2 or old Amount mol 1.8 0.5 ^ 0 duni compound 15 57264

Table 2 (continued)

Experiment Numbers Comparative Example 7 Comparative Example 8 Compare Read Example 9 *

Amount of 37 ~ 51 titanium or vanadium in the solid part in mg / g

Chlorine content of the solid mg / g 638 to 662

Organometallic compound EtyU. Et ^ Al Et ^ Al

Specific activity (g polymer / g Ti (V) h. C "2 atm) 53 000 1 130 28 300

Melt index 1.33 0.09 0.85

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Bulk density g / cm 0.28 0.08 0.12

Bigger than

Polymer 1 + 0 mesh weight- # 50.3 2l +, 7 18.2 particles „· ·,.

. . , Smaller than size. Distribution 2QQ mesh weight_ £ 2.5 1 +, 1 25.3

Experiment with Numbers Comparative Example 10

The carrier is MgCl 2 1 mol

Alcohol no Amount mol

Organometallic- Type Et, AI

compound _, 1, _- 3

Maara mol k x 10

Titanium or Type TiCl 2 vanadium compound, Amount mol 0.1

Amount of titanium or vanadium in the solid mg / g 10

Chlorine content of the solid part mg / g 770

The organometallic compound Et 2 Al

Specific activity (g polymer / g Ti (V) h.

C "2 atm) 1 + 50

Melt index 0.03

Bulk density g / cm 0.08

Greater than 1 + 0

Polymer mesh weight # 1 + 2.1 particles,, Less than 200 size distribution. . «, N Λ mesh weight # 0.9, 6 57264 * A titanium component prepared by filtering the solid product obtained from the reaction with EtgAlCl, washing the filtrate sufficiently with hexane, drying the product for 20 hours at 60 ° C and pressure was used. 1mmHg and reacting the dried product with TiCl 4 at 130 ° C, xx A titanium component prepared using Et 2 Al instead of Et 2 AlCl 2 used in Comparative Example 1 was used, further reacting the reaction product with titanium tetrachloride, removing excess titanium tetrachloride at 150 ° C under reduced pressure. ° C and heating the product for 3 hours at 300 ° C and 1 mmHg.

Example 5 A 2 liter autoclave was continuously fed hourly with 1 liter of hexane, 0.3 mmol of triethylaluminum, 0.03 mmol of the titanium catalyst component prepared in Example 1 calculated as a titanium atom and 220 g of ethylene containing 5 volumes of # butadiene at 80 ° C. hydrogen to give polymers with a melt index of 5 or 6, Polymerization continued effortlessly for 3 days, 200-210 g of Butadiene / ethylene copolymer were obtained per hour. The copolymer had a bulk density of 0.300 g / cm 3 and a melt index of 5.13. The specific activity was 70,000 g polymer / g Ti, h. The polymer contained 18.8 trans double bonds per 1,000 carbon atoms.

Example 6 To 1 liter of petroleum were added 0.0035 mol of the titanium catalyst component prepared in Example U, Experiment No. 6, calculated as a titanium atom, and 0.5 mmol of triethylaluminum. Hydrogen was introduced into the autoclave to give a total pressure of 2 3 kg / cm. Ethylene gas containing 0.5% by volume of n-butene-1 was continuously fed to a total pressure of 7 kg / cm 2 and polymerized for one hour to give 176 g of polyethylene having a melt index of 7.9 and a bulk density of 0.32 and containing 2 ethyl groups of 1,000 carbon atoms. towards. The specific activity was 50.300 g polymer / m Ti.h, which corresponded to 251.1 + 00 g polymer / g Ti x h C "^ atm. The particle size distribution was as follows:

Particle size Larger U2-60 60-100 100-150 150-200 Smaller (mesh) than 200

Distribution 5.1 6.7 51.5 26.0 7.0 3.7 (w / w) π 57264

Example 7

One mole of anhydrous magnesium dichloride was suspended in J liters of toluene, and 4 moles of each of the alcohols shown in Table 3 were added at a temperature of 1 + 0 ° C, followed by stirring the mixture for three hours. Each of the organometallic compounds shown in Table 3 was then added dropwise and the mixture was stirred for 2 hours. Titanium tetrachloride was then added and the mixture was stirred at 120 ° C for 2 hours. After the reaction, the reaction product was washed several times with toluene, 1 liter of petroleum, each of the organoaluminum compound shown in Table 3 and 0.01 mmol of the above titanium catalyst component calculated as a titanium atom were fed into a 2-liter glass vessel, and the mixture was heated to 90 ° C. Ethylene gas was introduced at atmospheric pressure and polymerized for 30 minutes. The results obtained are shown in Table 3.

18, 57264 S o o o S β o o

M · Η O O

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H ft O O

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H P bO

si 3 ^ P CO id d Ή · Η ft> e

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O

M id ft Ph ltn l / n P id H Λ Λ

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P ai di

EH · Η CU

β P · Η d CO ft J- d Ή ftp i — i p op S o o • H Hh S ή ή

Eh S P EH En id

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d · h as

P H

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Ph -H S PQ P

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ICO

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id o pr a s a • H S3 Sh

H O O

O · Η CM CM

-d ft 33 S3

O ft O O

ä 1 5.Q

d o age v ('§ § "" "~ d

• Ό) <H

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P <3 ft H H

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! § β

Claims (3)

A process for homopolymerizing or copolymerizing ethylene, propylene or a mixture of ethylene and a t-olefin and / or diolefin such as butadiene, ethylidene norborneene or dicyclopentadiene at a temperature of 20-200 ° C and a pressure of 1-100 kp / cm, optionally in the presence of hydrogen for adjusting the molecular weight, in the presence of a catalyst consisting of a) a transition metal catalyst component prepared by reacting a titanium or vanadium compound which is TiX 2, Ti (OF.) ·, VOX 2 or VX 2 in which X is a halogen atom, R is an alkyl group and r. is zero or a positive number less than U, and the reaction product obtained by reacting a solid magnesium dihalide support with an organometallic compound of the formula RM, RgM, Rg MgX, MAIR ^, R '^^ AIX ^ R' 2_nAl (OR) n or RA1 (OR) X, in which R is an alkyl or aryl group, M is a lithium, sodium or potassium atom, X is a halogen atom, p is zero or 1, R 'is a hydrogen atom or an alkyl or aryl group , m is zero or a positive number greater than zero but not greater than 3, and b) an organometallic compound catalyst component which is RJ_ A1X, R * Al (OR), RA1 (OR) X or R- MgX, in which RJ is a hydrogen atom 3-m m '3-n n' 2-p ^ p or an alkyl or aryl group, X is a halogen atom, m is zero or a positive number not greater than 3, n is a positive number , which is greater than zero but not greater than 3 and p is zero or 1, or a dialkylzinc compound, and wherein the transition metal compound the compound a) is present in an amount of 0.001 to 1,000 mmol, calculated as titanium or vanadium atoms per liter of an inert organic liquid medium or reaction zone, wherein the catalyst component b) is present in an amount of 1 to 10,000 moles per titanium or vanadium compound characterized in that said solid support is an adduct between magnesium dichloride or dibromide and a 1- or 2-membered aliphatic or aromatic alcohol having 1 to 12 carbon atoms, Process according to Claim 1, characterized in that the homopolymerization or copolymerization is carried out in an inert organic liquid medium. The catalyst composition used in the process according to claim 1 or 2, which consists of a) a transition metal catalyst component prepared by reacting a titanium or vanadium compound which is TiX 2, Ti (OR) 2 -XX, VOX 2 or VX 1 in which X is a halogen atom, R is an alkyl group and n is zero or a positive number less than U, and a reaction product obtained by reacting a solid magnesium dihalide support with an organometallic compound of the formula RM, RgMJ, R MgX 2, MAIR 4, R 12 -Al (OR) n or RA 1 (OR) X, wherein R is an alkyl or aryl group, M is a lithium, sodium or potassium atom, X is a halogen atom, p is zero or 1 , R 'is a hydrogen atom or an alkyl or aryl group, -.m is zero or a positive number greater than zero but not greater than 3, and b) an organometallic compound catalyst component which is R' A1X, R ' Al (OR), RAl (0R) X or R_ MgX, in which RJ is a hydrogen atom, or an alkyl or aryl group, X is a halogen atom, m is zero or a positive number not greater than 3, n is a positive number greater than zero but not greater than 3, and p is zero or 1, or a dialkylzinc compound, wherein the transition metal compound a) is present in an amount of 0.001 to 1,000 mmol calculated as titanium or vanadium atoms per liter of an inert organic liquid medium or reaction zone, and wherein the organometallic compound catalyst component b) is present 10,000 moles per mole of titanium or vanadium compound per titanium or vanadium atom, characterized in that said solid support is an adduct between magnesium dichloride or dibromide and a 1- or 2-membered aliphatic or aromatic alcohol having 1 to 12 carbon atoms. 21 57264