JPS6017368B2 - Catalyst manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for making a catalyst containing a transition metal product.

Polyolefins such as polyethylene, polyp.

In the production of pyrene, ethylene-butene copolymers, etc.
An important aspect of the various methods and catalysts used to make such polymers is productivity. Productivity is the amount or yield of solid polymer obtained by using a certain amount of catalyst. If the productivity is high enough, the amount of catalyst residue in the polymer is so low that the presence of catalyst residue has no negative impact on the properties of the polymer; No need to process. As is known to those skilled in the art, removing catalyst residues from polymers is an expensive process, and therefore it is desirable to use catalysts that provide sufficient productivity such that removal of catalyst residues is not necessary. Highly desirable. Additionally, high productivity is desirable to minimize catalyst costs.

Therefore, it is desirable to develop new and improved catalysts and polymerization methods that provide improved polymer productivity. According to the present disclosure, the transition metal product is formed from a metal dihalide compound and a transition metal compound.

Furthermore, according to the invention there is provided a method of manufacturing the above product.

Further, according to the present invention, there is provided a catalyst produced when the above product as a first catalyst component and an organometallic compound as a second catalyst component are mixed.

Furthermore, using the catalyst of the present invention, at least one polymerizable compound selected from aliphatic mono-1-olefins, conjugated diolefins and vinyl aromatic compounds is polymerized under polymerization conditions.

In a preferred embodiment, the catalyst is treated with a halogen ion exchange source and the polymerization reaction is carried out using an organometallic cocatalyst. Further, according to the present invention, the catalyst is prepared by mixing a metal halide compound and a transition metal compound in a suitable solvent to form a first catalyst component solution, heating and cooling the first catalyst component solution, and optionally preparing a first catalyst component solution. Undissolved substances are removed by filtration in an oven, and a second catalyst component solution containing an organometallic compound is added to the first catalyst component solution to avoid a significant temperature rise of the solution to mix the solid catalyst with the hydrocarbon solvent. It is prepared by forming a slurry, separating the solid catalyst from the slurry, washing with a hydrocarbon compound, and drying, all of the above steps being carried out essentially in the absence of air and water.

The present invention is based, at least in part, on the discovery of novel products formed from metal dihalides and transition metal compounds, wherein the metal of the metal dihalide is magnesium or zinc; The transition metal is titanium and the transition metal is bonded to at least one oxygen, nitrogen or sulfur atom, and the oxygen, nitrogen or sulfur atom is bonded to a carbon atom of the carbon-containing group.

Some suitable metal dihalides include, for example, magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium dichloride, zinc dichloride, and zinc difluoride. Among the metal dihalides, magnesium dihalide, especially magnesium dichloride, is preferred because it is easily available, relatively inexpensive, and provides excellent results.The metal dihalide component readily reacts with transition metal compounds. It is generally used as an anhydrous particulate solid to form a metal halide compound for use in accordance with the present invention using various techniques for converting the metal halide compound into a fine particulate form, such as roll milling, reprecipitation, etc. While it is recognized that the compounds can be tailored and that additional preparation of such metal halide compounds facilitates the reaction between the metal halide compound and the transition metal compound,
However, if the metal halide compound is in fine particulate form, there does not appear to be any difference in the catalysts of the invention prepared from the compositions of the invention, i.e., the productivity of the polymer is lower than that of the metal halide compound. It is not a function of particle size. The transition metal of the transition metal compound mentioned above is titanium. Excellent results have been obtained with titanium compounds and therefore titanium compounds are preferred. Some titanium compounds suitable for use in the present invention include, for example, titanium tetrahydrocarpyloxide, titanium tetramide, titanium tetraamide, and titanium tetramercaptide.
Metallic titanium tetrahydrocarbyl oxide is a preferred titanium compound because it provides excellent results and is readily available. Suitable titanium tetrahydrocarbyl oxide compounds include those represented by the formula: Ti(OR)4, where each R is individually an alkyl group having about 1 to 2 carbon atoms per group. , cycloalkyl, aryl, alkaryl and aralkyl hydrocarbon, and each R may be the same or different].

Titanium tetrahydrocarbyl oxides in which the hydrocarbyl groups contain from about 1 to about 1 solid carbon atom per group are most commonly used because they are more readily available. Suitable titanium tetrahydrocarbyl oxides include titanium tetramethoxide, titanium dimethoxy diethoxide, titanium tetraethoxide, titanium tetra-n
titanium tetrahexyl oxide, titanium tetrahexyl oxide, titanium tetradecyl oxide, titanium tetraeicosyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, titanium tetra-p-tolyl oxide and titanium tetraphenoxide. Among the titanium tetrahydrocarbyl oxides, titanium tetraalkoxides are generally preferred, and titanium tetraethoxide is particularly preferred because it provides excellent results.

Titanium tetraethoxide is also generally available at a reasonable cost. The molar ratio of transition metal compound to metal dihalide can be chosen over a relatively wide range.

Generally, this molar ratio ranges from about 10:1 to about 1:10, however, the most common molar ratio is about 2:1.
~about 1:2. When using titanium tetrahydrocarbyl oxide and magnesium dichloride to form the compositions of the present invention, a molar ratio of titanium to magnesium of about 2:1 is recommended in the present invention since it appears that all the magnesium compounds are readily soluble. be done. The metal dihalides and transition metal compounds used in the present invention are typically prepared, for example, by drying these two components (essentially in the absence of water) which is essentially inert to these components and the products formed. ) mixed by heating to reflux in a solvent or diluent.

"Inert" means that the solvent does not chemically react with dissolved components to interfere with product formation or the stability of the product once formed. Examples of such solvents or diluents include n-bentane, n-heptane, methylcyclohexane, toluene, xylene, and the like. It is emphasized that aromatic solvents, such as xylene, are preferred. The reason is that the solubility of metal halide compounds and transition metal compounds is higher than that of aliphatic solvents especially at low temperatures (described later), which is preferable when mixing metal halide compounds and transition metal compounds contained in a solvent with an organometallic compound. This is because they are also larger than aromatic solvents. Such mixing temperatures generally range from about 0 to about 1100°C, preferably about 115°C.
~14pi0. Also, the use of aromatic solvents, e.g. It is recognized that there appears to be an improvement in the production of large polymer particles and/or polymer particles with improved abrasion resistance. Generally, the amount of solvent or diluent used can be selected over a wide range. Typically, the amount of solvent or diluent will be from about 20 to about 100 cc per metal dihalide per night.
is within the range of The temperatures used during the heating process can also be chosen over a wide range. Typically, the heating temperature ranges from about 15 to about 15 degrees Celsius when the heating step is carried out at atmospheric pressure.
It is clear that when the working pressure is above atmospheric pressure, the working heating temperature becomes higher. The pressure used during the heating process does not appear to be an important parameter. In addition to the solvents or diluents mentioned above, more polar solvents or diluents, such as nitrobenzene and halogenated Hydrocarbons such as methylene chloride, chlorobenzene and 1,2-dichloroethane can be used. Generally, the time required to heat these two components ranges from about 5 minutes to about 1 field hour, although times from about 13 minutes to about 3 hours are sufficient in most cases. After the heating operation, the resulting solution can be filtered, if desired, to remove undissolved material or foreign solids. The dissolved composition of the invention thus produced can be obtained from a solvent or diluent by crystallization or other suitable means. It is also emphasized that the transition metal products of the invention are prepared in an oxygen-free system, such as in the absence of air, as well as in a dry system, ie, in the absence of water.

The compositions of the present invention are prepared using an oxygen-free nitrogen atmosphere, typically dry in a dry box, as is generally known in the art. Regarding the compositions of the present invention, examples are given below for illustrative purposes.

Example 1 (Preparation of first catalyst component) A composition of the present invention was prepared by reacting 2 moles of titanium tetraethoxide and 1 mole of magnesium monochloride in a hydrocarbon.

All mixing, filtering and washing operations were performed in a dry box under nitrogen atmosphere. 4.758 mmol (0.050 mol) of anhydrous magnesium dichloride powder was roll milled and 23.010 mmol. (
0.101 mol) of titanium tetraethoxide.

Under a nitrogen purge, the mixture was evacuated, heated to reflux temperature, refluxed for 48 minutes and cooled to room temperature to yield a solution containing very little undissolved residue. The reaction mixture was passed through a suction oven to remove residual bamboo, yielding a clear colorless solution. The solution contained in the flask was first cooled to about 0° C. using an ice cube, and then cooled to about -220° C. using a freezer to obtain a relatively small group of crystals. To increase the yield, the mother liquor was boiled under a nitrogen purge to evaporate about 1/3 of the volume. The resulting solution was cooled to room temperature, then to -220°C, and finally to about 78°C in a dry ice-impropanol bath.
Cooled for an hour. The mother liquor is pumped away from the resulting crystals, and the crystals are washed with about 17 to 20 ml of dry n-hexane cooled to 0.
The desk was cleaned three times using it each time. The liquid remaining after the final rinse was pumped off and the product was dried overnight under a nitrogen purge to give 23.6 g of white crystals, corresponding to 85% of the theoretical yield. Elemental analysis of a portion of the composition was performed with the following results (in weight percent): ○ Day ○ I Mg
Ti ○ Rational oblique 34.84 7.32 12
．． 85 4.4117.37 2321 Nao Minoru 32.
02 7.21 133 3.88 17.3 According to these results, it can be seen that a composition having a formula corresponding to 2ri(C02day5)4.M and 12 was produced and obtained.

It is therefore clear that this composition has a molar ratio of 2 moles of titanium to 1 mole of magnesium. A sample of white crystals was analyzed by powder X-ray diffraction under conditions excluding the presence of air and water.

This sample showed the following characteristics: Table 1 Planar spacing Spectrum of (meter ×
10-1o) Relative strength 10.77
Weak 10.47
very strong 9.28
very weak 8.73
Weak 8.23
very strong 8.10
Medium 7.91 Very strong 7.43 Strong 7.27
Strong 6.52
Weak 6-41
Weak 6.10 Weak 4
．． 90 Very weak 4.42
very weak 4.40
very weak 4.09
very weak 3.86
A very weak white t is the sun.

), it is clear that the composition has an essentially crystalline structure.

The crystal of the present invention is composed of two components.

The first catalyst component includes a composition as described above, and the second catalyst component includes an organometallic compound. Particularly effective catalysts have been obtained by treating the catalysts with halogen ion exchangers, such as titanium tetrahalide. For convenience, “Catalyst A
" means a catalyst that was not treated with a halogen ion exchange source, and "catalyst B" means a catalyst that was not treated with a halogen ion exchange source,
means a catalyst treated with In other words, catalyst B is
Catalyst A treated with a halogen ion exchange source. It has also been found that it is desirable to use catalyst A or catalyst B together with a cocatalyst containing an organometallic compound. The metal halide compounds and transition metal compounds suitable for preparing the compositions of the invention used as the first catalyst component of the invention have been described above, as well as the general and specific nature of the compositions.

It is recognized that the compositions of the invention do not need to be removed from the diluent or solvent, for example by crystallization, before being used in the preparation of the catalysts of the invention. Good results have been obtained by using the first catalyst component solution produced during the preparation of the composition and by using the composition of the invention taken out of the diluent or solvent. The second catalyst component is an organometallic compound, the metal being the first metal on the Mendeleev periodic table.
- selected from group m metals.

Some suitable organometallic compounds include, for example, lithium alkyls, Grignard reagents, dialkylmagnesium compounds, dialkylzinc compounds, organoaluminium compounds, and the like. The second catalyst component is generally an organoaluminum halide compound, such as a dihydrocarbyl aluminum monohalide of the formula R'2AIX, a dihydrocarbyl aluminum monohalide of the formula R'AI
X2 monohydro-rubyl aluminum. and hydrocaraluminum sesquihalides of the formula R' 2 x 3, where each R' is a straight-chain and branched hydrocarbyl having from 1 to about 20 carbon atoms per group. each X is a halogen atom and may be the same or different). Some suitable organoaluminum halide compounds include, for example, methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, Methyl-n-propylaluminum bromide, di-octylaluminum bromide, diphenylaluminum chloride, dicyclohexylaluminum bromide, jacosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride, ethylaluminum sesquiodide, etc. Good results have been obtained using ethylaluminum sesquichloride, ethylaluminum dichloride and diethylaluminium chloride;
Therefore, it is preferable. A preferred organoaluminum halide compound is ethylaluminum sesquichloride, which gave the best results. Although it is not necessary in all cases to use cocatalysts with the catalysts of the invention, the use of cocatalysts is recommended for best results. The organometallic cocatalysts suitable for use in the present invention are the same as the organometallic compounds suitable for use as the second component of the catalysts of the invention described above, and have the formula R″N
In addition to the organometallic compounds represented by Among the metal promoters, among the organometallic promoters, organoaluminum promoters are preferred, and in addition to those mentioned above as suitable for use as the second component of the catalyst, additional organoaluminums of formula R''3AI are preferred. Examples of compounds include trimethylaluminum, triethylaluminum, triisopropylaluminium, tridecylaluminum, trieicosylaluminum, tricyclohexylaluminum, triphenylaluminum, 2-
Methylbentyldethylaluminum and trisoprenylaluminum are mentioned. Triethylaluminum is preferred because it gave excellent results in the operations described below. The aforementioned metal halide compound/transition metal compound solution (
This may be formed by dissolving the removed composition of the invention in a suitable solvent, or it may be formed from scratch without removing the composition of the invention from the solvent.
is then contacted with a hydrocarbon solution containing the organometallic compound of the second component of the catalyst.

A solid reaction product precipitates out of solution. The molar ratio of the transition metal compound of the first catalyst component to the organometallic component of the second catalyst component can be chosen over a relatively wide range.

Generally, the molar ratio of the transition metal of the first catalyst component to the organometallic component of the second catalyst component ranges from about 10:1 to about 1:10, more typically from about 2:1 to about 1:3. is within the range of Molar ratios in the latter range usually produce catalysts that are particularly active for use as ethylene polymerization catalysts. The temperature used during mixing the first and second catalyst components described above can be selected over a wide range.

Generally, the temperature used is from about 1100°C to about 5°C or higher, with temperatures ranging from 110°C to about 30°C being most commonly used, but further research has shown that the first and second catalysts Using temperatures of about 100° C. to about 0° C. to mix the components produces larger polymer particles compared to the polymer obtained with the catalyst when the first and second catalyst components are mixed at temperatures above 0° C. It is surprising that it has been demonstrated that polymer particles with and/or improved abrasion resistance are produced. Therefore, as noted in the data below, polymer particles of good size were obtained by using mixing temperatures of about 115 to about 140 qo for the first and second catalyst components; A range of mixing temperatures is preferred. Because heat is generated when mixing the first and second catalyst components, the mixing speed is adjusted as necessary and additional cooling is used to maintain a relatively constant mixing temperature. Regarding the first and second components,
It is recognized that the order of addition is not critical and either component can be added to the other. After completing the mixing,
The resulting slurry is allowed to stand for a period sufficient to achieve complete mixing of the ingredients, generally from about 1 B minute to about 5 hours. Nawa Azusa.
It is recommended that the slurry be maintained at the mixing temperature for the first 10 to about 30 minutes after mixing and then gradually increase the temperature of the slurry to ambient temperature for the remainder of the time in the footbox. Thereafter, the enrichment is stopped and the solid product is obtained by filtration, filtration, etc. The product is then washed with a suitable substance such as a hydrocarbon such as n-pentane, n-heptane, cyclohexane, benzene, xylene, etc. to remove any soluble material that may be present. The product is then dried and stored under dry nitrogen. The product thus produced is referred to as catalyst A, as described above. In another aspect of the invention, catalyst A
The catalyst, referred to as Catalyst B, is treated with a halogen ion exchange source, such as a transition metal halide, to yield a catalyst with enhanced activity, previously designated Catalyst B.

Some examples of suitable halogen ion exchange sources used include titanium tetrachloride, vanadium oxychloride (VOC13
) and zirconium tetrachloride. Titanium tetrachloride is preferred because it is readily available and has given excellent results after some extensive experimentation. Generally, the treatment of the catalyst with the halogen ion cross-condensation source is carried out in a suitable diluent such as a hydrocarbon diluent such as n-pentane, n-heptane, cyclohexane, benzene, xylene, etc. to facilitate the treatment process. .

Processing temperatures can be selected over a relatively wide range, usually ranging from about 0 to about 20 pio, but surprisingly, catalyst A can be treated with a halogen ion exchange source to form catalyst B. Using a temperature of about 80 to about 180 degrees centigrade to process the polymer, the resulting Catalyst B produces larger polymers compared to catalyst B prepared at a lower processing temperature. It has been found and proposed that coalesced particles and/or polymeric particles with improved abrasion resistance can be produced. In view of the foregoing findings, the preferred treatment temperature for treating catalyst A with a halogen ion exchange source is:
Approximately 100 to 130q when considering overall catalyst performance
It is o. Use of processing temperatures above 13 pm, such as temperatures between 150 pm and about 180 pm, results in polymer particles that are larger and/or ) Catalysts made at processing temperatures of about 150 to about 180 qo, which produce more abrasion resistant polymer particles,
and also exhibit significantly reduced productivity compared to catalysts produced at lower processing temperatures.

Particularly good results are obtained when Catalyst A is prepared using a low mixing temperature for mixing the first and second catalyst components as described above and is then treated with a halogen ion exchange source using a high processing temperature as described above. The results obtained are also noteworthy. For example, a mixing temperature of about 0 to about 100° C. is used to mix the first and second catalyst components to produce catalyst A (preferably in an aromatic solvent), and then the halogen ion exchange of catalyst A is performed. Approximately 80~ for processing by Mo Kengen
Using a processing temperature of about 180°C, particularly large and (
or) a catalyst is obtained which provides abrasion resistant polymer particles. Treatment times can also be selected over a wide range and generally range from about 10 minutes to about 1 time.

Although the weight ratio of halogen ion exchange source to catalyst A can be selected over a relatively wide range, the weight ratio of halogen ion exchange source to catalyst A is generally from about 10:1 to about 1.
:10, more typically from about 7:1 to about 1:4. After treating catalyst A with a halogen ion exchange source, a super-rich halogen ion exchange source (a halogen ion exchange source that does not combine with catalyst B) converts catalyst B into a dry (essentially absent of water) liquid, such as carbonization of the type described above. Hydrogen is removed by washing with n-hexane or xylene. The resulting product, catalyst B, is stored under dry nitrogen after drying. Catalyst B remains active for one month or more;
It was found that the product could be stored and released without any deterioration, and was released.

If desired, catalyst A or catalyst B is mixed with particulate diluents such as silica, silica alumina, silica titania, magnesium dichloride, magnesium oxide, polyethylene, polypropylene and polyphenylene sulfide before using the catalyst in the polymerization step. There are things you can do. Although the weight ratio of particulate diluent to catalyst can be selected over a relatively wide range, the weight ratio of particulate diluent to catalyst is generally about 100:1.
to about 1:100. More often, the weight ratio of particulate diluent to catalyst ranges from about 20:1 to about 2:1, with the use of particulate diluent being effective to facilitate loading the catalyst into the reactor. It was found that it was, and it was released. The molar ratio of the organometallic compound of the cocatalyst to the transition metal compound of the first catalyst component is not particularly critical and can be chosen over a relatively wide range.

Generally, the molar ratio of the organometallic compound of the cocatalyst to the transition metal component of the first soot component ranges from about 1:1 to about 1500:1. However, in general, using a relatively large amount of cocatalyst relative to the catalyst will result in larger and/or
It has been found that polymer particles with greater abrasion resistance can be produced. For example, at least about 4:1 to about 40
Cocatalyst to catalyst weight ratios of 0:1 and higher produce larger and/or more rub-resistant particles, but generally the higher the cocatalyst level, the more It was found that the polymer yield per unit weight of was lower and was therefore given as the best compromise between particle size and/or abrasion resistance and polymer yield of about 6:
A cocatalyst to catalyst weight ratio of 1 to about 100:1 is generally recommended. Olefins that can be mophopolymerized or copolymerized using the catalyst obtained by the method of the present invention include aliphatic mono-olefins.

Although the catalyst obtained by the process of the invention is believed to be suitable for use with any aliphatic mono-1-olefin,
It is most commonly used for olefins having 2 to 18 carbon atoms. Mono-1-olefins can be polymerized using particle or solution methods. Aliphatic mono-1-olefins may contain other 1-olefins and/or other ethylenically unsaturated monomers in lesser amounts such as butadiene-1,3, isoprene, bentadiene-1,3, styrene, alpha-methylstyrene. and similar ethylenically unsaturated monomers that do not damage the catalyst. The catalyst obtained by the process of the invention can also be used to produce homopolymers and copolymers of conjugated diolefins.

Generally, conjugated diolefins contain 4 to 8 carbon atoms per molecule. Examples of suitable conjugated diolefins include:
1,3-putadiene, isoprene, 2-methyl-1,3
-butadiene, 1,3-pentadiene and 1,3-octadiene. In addition to the conjugated diolefins mentioned above, suitable como/mers generally include the mono-olefins and pinyl aromatics mentioned above. Some suitable pinyl aromatic compounds contain about 8 to about 14 pinyl aromatic compounds per molecule.
Examples include styrene and various alkylstyrenes such as 4-ethylstyrene and 1-vinylnaphthalene. The weight percentage of conjugated diolefin in the copolymerization mixture can be selected over a relatively wide range.

Generally, the weight percent of the conjugated diolefin is from about 10 to about 95 weight percent and the other comonomer is from about 90 to about 5 weight percent. However, the weight percent of the conjugated diolefin is approximately 50
~9% by weight, and the other comonomers are ~50% by weight.
Preferably it is about 1% by weight. The catalyst obtained by the process of the invention was found to be particularly effective for the polymerization of mono-1-olefins such as ethylene (remarkably high productivity was obtained) and therefore
Olefins are the preferred monomers used for the catalyst obtained by the process of the invention. Polymerization methods using the catalysts and cocatalysts described above can be carried out batchwise or continuously.

In the batch method, for example, an autoclave with a
It is prepared by first purging with nitrogen and then with a suitable compound such as isobutane. If a catalyst and cocatalyst are used, either can be charged to the reactor first or both can be charged simultaneously from the inlet under isobutane. After closing the inlet, hydrogen, if used, is added and then a diluent, such as isobutane, is added to the reactor. The reactor is heated to the desired reaction temperature, typically about 50
heating to a temperature of ~120°C and then introducing ethylene;
Approximately 5/10 to approximately 5.0 MPa (
70-725 psig). At the end of the indicated reaction period, the polymerization reaction is stopped and unreacted olefin and isobutene are discharged. The reactor is opened and the polymer, such as polyethylene, is collected as a free-flowing white solid and dried to yield the product. In a continuous process, for example, a suitable reactor, such as a loop reactor, is continuously charged with suitable amounts of solvent or diluent, catalyst, cocatalyst, polymerizable compound, and hydrogen, if used, in any desired order. The reactor product is continuously withdrawn, the polymer is generally obtained by flashing to remove diluent (solvent) and unreacted monomers, and the resulting polymer is optionally obtained by drying. Olefin polymers produced using the catalysts obtained by the process of the present invention are useful for producing articles by conventional polyolefin processing techniques such as injection molding, rotational molding, film extrusion, and the like.

For example, polyethylene produced using the catalyst obtained by the process of the invention typifies a narrow molecular weight distribution that is particularly desirable for injection molding applications. Additionally, the manufactured polyethylene produced as described above generally has a desirable high bulk density of about 0.44 m/cc when obtained from a polymerization belt. Furthermore, the polyethylene is characterized by a high degree of stiffness, such as a high flexural modulus, which is also desirable in many applications. Example 2 Catalyst Preparation Catalyst A All mixing and furnace operations were carried out in a dry box (essential absence of air or oxygen and water) under a dry nitrogen atmosphere using dry n-hebutane as the reaction medium.

Magnesium chloride and titanium tetraethoxide (unless otherwise noted) were charged to a flask equipped with equipment for refluxing the contents and for a rope frame. The mixture was raised to reflux temperature (approximately 100° C.), refluxed for the times shown in Table 2, cooled, and filtered if foreign or undissolved material was present. The product was cooled in an ice bath and the indicated organoaluminum halide compound was added to the product at a rate sufficient to avoid appreciable temperature rise to form a slurry. Approximately 30 minutes after removing the flask from the ice rack, the resulting slurry was poured. The slurry was filtered to yield a filter cake, which was washed several times with dry n-hexane and dried under a nitrogen purge to yield the product. The amounts of substances used, the weights and molar ratios of reactants charged, and the results obtained are shown in Table 2.
Shown below. Table 2 Pressure: (1) Ti (0 ratio)4. Square shaft certain A-1 to A-8 and A
-10 at'ri (002 days 5) 4. Ti with square bag plan A-9
1○n-04th 9) 4(2) HABO is 25wt. in n-beftane. The abbreviation is ethylaluminum sesquichloride.

(3) HADO was 25 wt. in n-hexane. *This is ethyl aluminum chloride. ■ UHAO is n-
12.96 wt. in hexane. This is my grandson's ethyl aluminum chloride. (5) i-BADO is 25.4 wt. in n-hexane. It's isobutylaluminum chloride. ■ n-hexane (7) n-hebutane Example 3 Catalyst Preparation Catalyst B All mixing and filtration operations were carried out in a dry box under nitrogen atmosphere using dry n-hexane as reaction medium.

N-hexane, catalyst A were added to a flask equipped with a rope azusa device.
and titanium tetrachloride. Generally, each mixture was allowed to stand for about 1 hour at a temperature of about 2° C. and then roasted. The filter cake was washed several times with dry n-hexane and dried under a nitrogen purge. 50 dry matter unproducts
Passed through a mesh to remove larger particles. The amounts of components used, the weight ratio of Catalyst A to TIC14 and the results obtained are shown in Table 3.

Table 3 Notes... ■ The product obtained at 21.040 pm was 50 mesh fine polyethylene 84.054 dried in a vacuum oven.
Dilute in the evening. This mixture was roll milled overnight (approximately 13 hours).

The mixed catalyst comprises about 1 part by weight of active ingredient and 4 parts by weight of diluent. This mixture was kept under N2. (9)
27.498 pm acquisition product. 108.502 ml of finely dried polyethylene and processed as described in (8) above. This mixture was kept under N2. The mixed catalyst consists of approximately 1 part by weight of active ingredient and 3.95 parts by weight of diluent. Catalysts A-2 and B-2 (not mixed with finely divided polyethylene) were subjected to elemental analysis. The obtained results are summarized for each element. The amount of oxygen is shown below in %: {10
It was determined by subtracting the total weight of all components from the total weight of the catalyst sample.

The above results indicate that the treatment of catalyst A composition with TIC141 exerts a certain effect on the elements constituting the composition.

The Ti concentration was 1.1wt. % increase, and the chlorine concentration increased by 15. shoes t. % increased, but especially carbon, hydrogen and oxygen decreased. From the above results, it is believed that the halogen ion exchange source, in this case titanium tetrachloride, causes the exchange of chloride with the ethoxide groups in the catalyst.

In addition, catalysts A-2 and B-2 were analyzed by powder X-ray diffraction and
The test composition and bulk crystal phase were investigated by line photoelectron spectroscopy.

As a result, no significant difference was observed in the elemental composition of the surface within experimental error.

However, catalyst B-2 appears to be amorphous;
Catalyst A-2, on the other hand, appeared to have a highly crystalline component with low surface area. Example 4 Ethylene Polymerization 3.8 Ethylene was polymerized using a stainless steel reactor with a rope sieve.

The reactor was charged with 30% dry n-heptane for each operation, the inlet was closed, and the reactor and contents were heated to 30% at 175q0.
Adjust by heating for a minute. The reactor was drained and purged with dry nitrogen to remove residual hebutane. The reactor was then closed and cooled under nitrogen pressure. The conditioned reactor was purged with dry isobutane vapor and 15M. %(2.
Three cocatalyst solutions containing 8 mol) of triethylene aluminum (TEA) were charged and then the catalyst was added.

Close the reactor and charge about 2.1 hours of dry isobutane,
The reactor and contents were heated to 80°C and ethylene and hydrogen (if used) were added. Each run was stopped by flushing the reactor of ethylene and isobutane and hydrogen if present. The polymer was then obtained, dried and weighed to obtain the yield. Each polymer yield was divided by the weight of catalyst used to determine the calculated catalyst productivity as k9 of polyethylene per catalyst per hour per evening.

For some operations below 60 minutes, productivity figures are calculated based on reasonable assumptions based on past experience that catalyst activity remains unchanged for at least the first 60 minutes of each operation. Calculate carefully.

If the catalyst is diluted, k9 of polyethylene produced per evening of diluted catalyst per hour and k9 of polyethylene produced per evening of catalyst included in the mixture per hour.
It shows the computational productivity based on g. Table 4 shows the amount of each catalyst used, operating time, working pressure, and the results obtained.

Table 4: 1I) Dilute 1 part by weight of catalyst with 4 parts by weight of polyethylene powder; calculated productivity is 5 x 29.3 or 147&polymer/ta undiluted catalyst.

(12) 30 minutes operation time. Computational productivity is 54.4×6
Q3) 30 minutes operating time which is 0÷30K/catalyst or 109&/tacatalyst/hour. Calculation productivity is 60×60÷3
0 &/ta catalyst or 120 &/ta catalyst/hour.

(14) 40 minutes operation time, calculation productivity is 83.1 x 60
÷40 &/ta catalyst or 125 ship/ta catalyst/hour.

15) 45 minutes operation time, calculation productivity is 66.7 x 6
0÷45&/tacatalyst/hour. 16) Dilute 1 part by weight of catalyst with 3.95 parts by weight of polyethylene powder: the calculation is 4.95 x 7,36 or 36.4 x polymer/ta undiluted catalyst. u7) 40 minutes of crop time, calculation productivity is 55
．． According to the results in Table 4, although catalyst A is relatively active for ethylene polymerization, the corresponding catalyst A
It is noted that catalyst B is not as active as catalyst B formed by TIC14 treatment.

kg of polyethylene produced per evening of catalyst per hour
As indicated, catalyst A generally yields polymers of about 3-36k9, but its corresponding catalyst B generally yields polymers of about 36-210k9.

In this regard, catalysts B-6 and B-7 (operations 18 and 19) correspond to the corresponding catalyst "A" or catalyst A-6.
It is noted that the productivity is very high compared to A-7 and A-7 (Runs 6 and 7). The best results under the conditions of use were obtained with catalyst B-1, which is prepared by treating catalyst A-1 crude prepared from the titanium ethoxide magnesium dichloride reaction product with chelaluminum sesquichloride.
Obtained in operation 21 using 0.

This catalyst was extremely active, yielding 210 k9 of polyethylene per night of catalyst per hour. Example 5 Catalyst Preparation Catalyst A All mixing and furnace operations were carried out in a dry box under an argon atmosphere using dry hydrocarbons as the reaction medium.

Anhydrous magnesium dichloride and titanium tetraethoxide were charged to a flask equipped with reflux and clarification equipment and containing the selected reaction medium. Each mixture was heated at the temperature and time indicated in Table 5 and cooled to the temperature indicated for the dropwise addition of a 0.783 mol n-butane solution of ethylaluminum sesquichloride. The resulting slurry was generally mixed with three more powders after completion of the reaction, the hydration was stopped, and the mixture was allowed to flood to room temperature if cooling was used. The slurry was filtered through a suction oven to produce a filter cake, which was washed several times with dry n-hexane and dried under an argon purge to yield the product. The amounts of materials used, the weights and molar ratios of reactants charged and the results obtained are shown in Table 5. Table 5 (a) Several batches of catalyst were made under the conditions indicated. K these together and call it A-16.

(b) 200% Killen K addition, Mg0 SO2, cooled to -26°C and kept in a dry & dry bath.
/TiLOO 2 days 5) solution at 25. Cool CK. Next, a solution of HAS○ was added dropwise. (c) Clean the filter casing with 50 female sterilizers. Next, wash with 250 Iso n-hexaso.

b) Use 4.57 pieces each. Remove liquid from the product after each addition. Example 6 Catalyst Preparation Catalyst B All mixing and filtration were carried out in a dry box under an argon atmosphere using dry n-hexane as the reaction medium.

A flask equipped with a reflux system was charged with n-hexane, Catalyst A from Example 5, and titanium tetrachloride.
Soaking each mixture at the temperature and time indicated in Table 6;
If necessary, it was cooled to room temperature and then passed through a suction oven. The filter cake was washed several times with dry n-hexane and dried under an argon purge. Amounts of components used, Catalyst A vs. TIC14
The weight ratios and the results obtained are shown in Table 6. 6. Sho: (a) Estimated Example 7 Ethylene Polymerization Ethylene polymerization was carried out using a stainless steel reactor equipped with a 3.8-meter key azusa bag, which was prepared as in Example 4 above.

For each run, the conditioned reactor was purged with dry isobutane vapor and IM. % (0.93 mol) of triethylaluminum (TEA) was charged and then the catalyst was added.

The reactor was closed, charged with approximately 2 cm of dry isobutane, the reactor and contents were heated to 80°C, and ethylene was added.
There is no hydrogen present in either operation, so
Each of the produced polymers had a melt index of less than 0.5. Unless otherwise specified in Table 7, an operating time of 60 minutes was observed for each operation. Similarly to example 4,
Each operation was stopped and a polymer was obtained.

If an operating time of less than 60 minutes is used, use the calculated productivity numbers for 60 minutes as in Example 4.

As-manufactured and as-manufactured Waring blenders
The particle size distribution of the obtained polymer in the ground state was determined by rolling approximately 100 grams of the polymer onto a set of mechanically tied knots.

Node sets consisted of nodes with mesh sizes of 30, 50, 80, 100, 200 (U.S. age series) and basal blood. Brushing was carried out for 30 minutes unless otherwise specified, and the amount of polymer remaining on each plate and dish was weighed. The ground sample was blended in a Waring blender for 2 minutes at high speed at room temperature. The purpose of milling the as-produced polymer is to mimic the friction that polymer particles would experience in a large scale reactor, such as a loop reactor. After all, commercially formed polymer particles generally suffer from a substantial decline in the production of finer particles compared to polymer particles produced at the industrial scale. This is because that. Grinding of the polymer with a Waring blender as previously described and throughout the text was carried out using a dry polymer flake (100 μH) at DyMmICS Corporation, New Hartford, CT.
ion of America, Waring Pro
This is done by grinding for 2 minutes at room temperature (25° C.) on a Waring Plender Model 31DL42 manufactured by ductsDMsion at maximum speed.

Although any mill or blender suitable for vigorously grinding relatively small amounts of polymer can be used, most
The Waring Plender mentioned above has a very good effect.
Gave. The ground fluff is then sieved for 15 minutes.

Ohio, Cleveland, U.S. S. TylerN
Electric Ro-T manufactured by Nenyama Actming Company
An AP cutting machine was used, but most any cutting machine could be used or the polymer could be cut by hand. Table 7 shows the usage of each catalyst and the results obtained.

In each run, the initial ethylene pressure was 0.69 MPa (Satoshi.5 psig), and the average total pressure for all runs was 1.5 psig. gkepa (271.4psi
g) except that in steps 24 and 26 2. The plate Mpa was 285.7 psig.

Table 7 (a) Polymer per hour of catalyst per night.

(b) A run time of 36 minutes gives 507 minutes of polymer. Productivity for 60 minutes is 149.1 &/evening/36 minutes x
Calculated as 60 minutes ÷ 36 minutes or 248.5 &/evening/60 minutes.

(c) A run time of 40 minutes gives 573 minutes of polymer. Productivity for 60 minutes is 108.1 &/evening/40 minutes x
Calculated as 60 minutes ÷ 40 minutes or 162.1st/evening/60 minutes.

(d) A 15-minute set prayer was used. (e) - indicates not measured.

(f) Analytical reagent grade. 137 to 144°C boiling point. Examination of the results shown in Table 7 shows that the reaction conditions used for the type of catalyst are important in terms of productivity of polymer produced per unit weight of catalyst per hour and particle size distribution of the polymer. It turns out that. The most productive catalysts are as shown in operations 22-24, where catalyst A is formed in a paraffinic reaction medium at about 125°C to about 2.5°C, and then catalyst A is
It appears to be obtained when the final catalyst (catalyst B) is formed by contacting with C14 at about 100 to about 125°C. These catalysts contain particles coarser than 100 mesh, approximately 8 mm. % of the as-prepared relatively targeted polymer. However, the amount of coarse polymer remaining after grinding in a Waring blender for 2 minutes is about 45-60M particles coarser than 100 mesh. %, the polymer has some brittle properties. Catalyst A in an aromatic reaction medium of about 120
-25 qo and forming catalyst B by contacting catalyst A with TIC14 at about 80 to 180 qo, the powder size of the as-produced and milled polymers is as follows in steps 25-29. Rough as evidenced by the results.

The coarsest and most abrasion resistant polymer was made with Catalyst B, which was formed by contacting TIC14 at 180°C. However, the productivity of this catalyst is
-29 was substantially lower compared to other catalysts. Operation 2
According to the data in 5-29, when catalyst A is formed at about 125 qo and then catalyst B is formed from catalyst A at about 80 to about 130°C, the catalyst B is formed by slurry polymerization using a coarse friction-resistant polymer. It turns out that it is possible to produce at high speed. All of the polymers shown in Table 7 were tested under ASTM Town 2-1 65T Condition E.
It has a relatively low melt index value of less than about 0.5, as measured by the method of .

Example 8 Ethylene Polymerization - Effect of Catalyst Level Ethylene polymerization was carried out using a stainless steel reactor equipped with a 3.8 rope scaler prepared as in Example 4.

The reactor prepared for each run was purged with dry isobutane and 15M. % of triethylaluminum (TEA) was charged in the indicated amount and then the catalyst was added.

A portion of catalyst B-16 was used in each run. The reactor was closed and charged with approximately 2 kg of dry isobutane, the reactor and contents were heated to 100° C., and ethylene and hydrocarbons were charged. An operating time of 6 minutes was used.

In the same manner as in Example 4, each operation was stopped and a polymer was obtained.

The fineness distribution of the as-produced polymer and the produced and milled polymer was determined as in Example 7. Table 8 shows the amounts of each catalyst and cocatalyst used, the melt index of each polymer, and the results obtained.

In each operation, the initial hydrogen pressure was 0.34 Mpa (5 Capes
ig), the initial ethylene pressure is 1.4 Mpa (20 cape aig), and the total pressure reached during the polymerization is 3.3
3.4Mp excluding operation 35 of Mpa (48 tsubo sig)
a (50 cape sig).

Table 8 G) 2ppm based on the weight of any isobukun (1100 yen).

(bJ MI is melt index.8/10 minutes.AS
TMD1238-65T. Condition date. (c) HLMI is High Load Melt Index, g/10 min. ASTMD1
238-65T, condition F. The relative LMI seems to be related to the molecular weight distribution. The larger the value, the broader the molecular weight distribution. (d) The level of T8A cocatalyst used in the operation is. The approximate molar ratio of TEA to Ti in the above catalyst is about 1
0:1 to about 450:1.

(e) - indicates that the measurement has not yet been made. The data shown in Table 8 shows that as-produced coarse particles are produced at all cocatalyst usage levels.
According to the trends observed in operations 31-38, based on the milled polymer results, it can be seen that increasing cocatalyst levels produce polymers with greater rub resistance. At the same time, however, catalyst productivity appears to decrease somewhat as cocatalyst levels increase. Since the aluminum alkyl cocatalyst is a relatively expensive material, it is desirable to use up to 4.5% of the cocatalyst, consistent with high polymer productivity and low catalyst residue and production of rub resistant polymers. . According to the above results, the cocatalyst level is about 20 to 20 TE
A (promoter to catalyst weight ratio of about 4:1 to about 40:1), more preferably about 30 to 10 cocatalysts (promoter to catalyst weight ratio of about 6:1 to 35:1); It can be seen that the above objectives can be achieved with the substances and conditions used. Melt index measurements of the resulting polymer demonstrate that a commercially useful material is produced.

This is because the polymer's lug index ranges from 0.4 to 4 for many applications including films, sheets, pipes, bottles, and containers. HLMI shown
/MI ratio indicates a relatively narrow molecular weight distribution polymer. Ethylene polymers with such a molecular weight distribution are particularly suitable for injection molding. Example 9 A Catalyst Preparation (Catalyst A) B Catalyst Preparation (Catalyst B) C Ethylene Polymerization A in the Presence of Hydrogen A series of catalysts A were prepared generally as in Example 5.

The amounts of reactants used, the reaction conditions used, and the results obtained are shown in Table 9. B Catalyst B was prepared generally as in Example 6 by postcontacting a weighed portion of Series A with Tic14. The amounts of reactants used, the reaction conditions used and the results obtained are shown in the table. A series of ethylene polymerization operations were carried out generally as in Example 7 using each catalyst B shown in Omotesou. However, each practical run was performed in the presence of hydrogen to produce higher melt index polymers. The produced polymer and usage conditions are shown in the table. table
9A Table 9B 90 (a) The operation time is 2% time. Productivity is &/evening/2
% time.

(b) The operation time is 2 hours and the productivity is &/evening/2 hours. (c) Absolute pressure. The effects of low mixing temperatures and high processing temperatures on the modified catalysts of the present invention with respect to polymer particle size and abrasion resistance are shown in the results of the operations shown in Table 7 in which low melt index polymers are produced and comparatively. The table in which high melt index polymers are produced is demonstrated in operations 44-47 of the present invention.

Grinding tests performed on polymers formed using catalysts obtained by the process of the present invention have shown that polymer melt indexes of about 1 or higher result in less coarse (fine) polymers. Observed from past experience. It also appears that a leveling effect occurs when the melt index ranges from about 5 to at least about 40. The amount of coarse polymer after milling is generally from about 80 to about 96 wt. for low melt index polymers. % and about 60-70 wt.% for high melt index polymers. %. Therefore, on a laboratory scale, relatively high melt index polymers (approximately 5 to
It is currently believed that a catalyst can be more accurately evaluated for possible commercial use (commercial operations) by preparing a 40 melt index. Comparing the results of operations 39-42 and 44-47 in the table, it is generally found that a solution of Ti(OR)4-MgC12 in paraffin, e.g. Catalysts prepared by treating the separated particulate product with TiD14 at room temperature or above yield relatively less coarse polymers (more finely tuned) compared to the preferred catalysts obtained by the method of the present invention. I understand.

Therefore, preferred catalysts obtained by the process of the present invention which yield large and rub-resistant polymers use aromatic solvents and low temperatures (0 to 110 pi) to prepare catalyst A and B is formed by using elevated temperatures (80-180°C) to produce B.

The lower temperatures used in the preparation of catalyst A are advantageous in reducing fines (enhancing coarser polymer particles) in the final catalytic polymerization operation. This condition favors the production of catalyst particles that are uniform in size and generally spherical. The elevated temperature used to form Catalyst B appears to harden the Catalyst A particles. The overall effect results in a catalyst that can produce spherical polymers with great abrasion resistance and with very high polymer productivity. 1.33 evenings in a bottle (
0.00976 mol) of ZnC12, 3 ml of n-hexane, 4.55 ml (0.020 mol) of Ti(OEt
) 4 and 20' dry tetrahydrofuran (THF)
I put it in.

The pin and its contents were heated to about 80 qo to yield a two-phase solution/slurry mixture. At that point, an additional 10' THF
was added to form a solution. Leave the solution for another 10 minutes at 80°C.
q0, then cool it to about 55 qo, 12
[(
0.020 mol). Approximately 50% of the resulting slurry
At 05:00, the mixture was hawked for 48 minutes, cooled to about 360℃, and filtered under suction to obtain black Hashiwa liquid and Hijiri-colored Sarutsu. Wataritsu was washed with 100% of n-hexane, dried under a stream of argon, and washed with catalyst A.
5.52 times of fringe powder was produced as 128. 2.0
Evening catalyst A-28, 20 [n-hexane and 4] [
(The slurry formed from TIC14 on the evening of June 9th was roped at about 2,500 yen for one hour.

The obtained product was suction filtered to obtain a yellow liquid and a brown liquid. The birch was washed with 50 liters of n-hexane and dried under a stream of argon to produce a light tan powder of 2.49 g. This was designated as catalyst B-28. Before starting the catalyst preparation using MgBr2, it was necessary to dehydrate the commercially available MgBr2 SLO.

500 ml of hydrated salt in the flask and about 350 ml of it
1400' of absolute alcohol was added.

The water is partially removed and most of the ethanol is removed as an ethanol-water azeotrope by fractional distillation, after which approximately
M of n-hebutane was added to the flask and the remaining portion of the water was removed as a water-ethanol-n-hebutane ternary azeotrope and the excess ethanol-n-hebutane azeotrope was removed. The distillation was stopped, the clear n-heptane was removed by filtration, the remaining n-heptane was removed under reduced pressure, and the honey water M
left a white solid as r2. The solid was actually MgBr2 alcoholate formed during the process. 2
．． 30 moles (0.012 moles) of M2 alcoholate were placed in a bottle, 40 moles of dry TEF and 5.40 moles (0.0 moles) were added to the bottle.
24 mol) of Ti(ORt)4 was added to form a slurry.

The slurry was heated at 110° C. for 5 minutes to form a solution. The solution was then cooled to about 25°C and treated with (0.024 mol) of 0.8M dibutylmagnesium solution 40 for 15 minutes. 6 bottles of slurry
000 and further treated over 0.8M dibutylmagnesium solution 40 for 13 minutes. The resulting slurry product was further stirred at 60°C for 4 minutes to give a volume of about 25q0
The liquid was cooled to obtain absorbed liquid and black liquid. 100 monkeys
After washing with n-hexane and drying in a stream of argon, a black powder 505 was obtained. This was designated as catalyst A-29. 2.
Catalyst A-29 at 0 tm, 20 ts n-hexane and 4 ts (
A slurry formed from TIC14 of 6.9% was pitched at about 25 qo for 1 hour. Next, the slurry was passed through a vacuum filter to obtain a pale yellow solution and a black solution.

The solution was purified with 100% of this n-hexane and dried in a stream of argon to give 2.36% of a black powder. This is the catalyst B-
29. Polymerization experiments were carried out at 90° C. for 1 hour with an ethylene/1-butene partial pressure of 0.69 megapascals (M yen a) and 0.17 moles of hydrogen and a total reactor pressure of 2.38 MPa.

IM's TEA solution 1 skin was used as a cocatalyst in the experiment. After charging the isobutane to the reaction, 49 g of 1-butene was pumped into the reactor. The remaining ingredients were then added in the same order and the polymer was separated in the same manner as described for ethylene polymerization. Melt index value according to ASTM D1238-
65T, condition E. ASTM density value
Determined according to the D1505 route. Ethylene/1-butene copolymerization (Sho) (a) Amount of polymer per hour per catalyst per night (&)
The above results show that by following the formulas of the present invention, active catalysts for ethylene homopolymerization and ethylene/1-olefin copolymerization can be obtained.

Claims (1)

[Scope of Claims] 1 (A) dihalide of magnesium or zinc;
B) of the formula Ti(OR)_4, where each R may be the same or different and is an alkyl, cycloalkyl, aryl, alkaryl or aralkyl hydrocarbon radical having 1 to 20 carbon atoms; A first catalyst component is formed by reacting the first catalyst component with a transition metal compound having a precipitant which is an organometallic compound of magnesium or aluminum, and then the first catalyst component is reacted with a second catalyst component consisting of a precipitant which is an organometallic compound of magnesium or aluminum. A method for producing a catalyst, characterized in that the solid product is treated with a halide of titanium as a source of halide ion exchange. 2. The method of claim 1, wherein the halide ion exchange source is titanium tetrahalide. 3. The method according to claim 1 or 2, wherein the halide ion exchange source is titanium tetrachloride. 4 The transition metal compound of component (B) has the general formula Ti(OR)
Claims 1 to 3, which are titanium compounds of _4 (in the formula, each R may be the same or different and are an alkyl radical having 1 to 10 carbon atoms)
The method described in any one of paragraphs. 5 The transition metal compound is titanium tetraethoxide,
A method according to claim 4. 6. The method according to any one of claims 1 to 5, wherein the metal dihalide of component (A) is magnesium dichloride. 7 The second catalyst component has the formula R'AlX_2, R'_2AlX, or R'_3Al_2X_3, where each R' can be the same or different and has a straight or branched chain having from 1 to 20 carbon atoms. The method according to any one of claims 1 to 6, wherein the hydrocarbon aluminum halide is a hydrocarbon radical and X is a halogen atom. 8. The method of claim 7, wherein the second catalyst component is ethylaluminum sesquichloride. 9. Reacting components (A) and (B) to form a first catalyst component in a hydrocarbon solvent, and exposing the first and second catalyst components to each other at a temperature within the range of -100°C to 0°C. and contacting the solid product resulting from the combination of the first and second catalyst components with a halide ion exchange source at a temperature within the range of 80°C to 180°C.
The method according to any one of paragraph 8. 10 Heat the first and second catalyst components at -150°C to -40°C.
10. A method according to claim 9, wherein the contacting is carried out at a temperature within the range of . 11 The hydrocarbon solvent is aromatic and the treatment with the halide ion exchange source is carried out at a temperature within the range of 100°C to 130°C. A method according to claim 9 or 10. 1
2 Transition metal pair component (A) of the transition metal compound of component (B)
) has a metal molar ratio of 10:1 to 1 in the metal halide compound.
:10, and the molar ratio of the transition metal of the transition metal compound of component (B) to the second catalyst component is 10:1 to 1:10.
A method according to any one of claims 1 to 11. 13 The above molar ratios are 2:1 to 1:2 and 2:
13. The method of claim 12, wherein the ratio is 1 to 1:3. 14 Claims 1 to 1, wherein the weight ratio of the halide ion exchange source to the total weight of the source catalyst is from 7:1 to 1:4.
3. The method according to any one of 3. 15. The method according to claim 6, wherein the transition metal compound of component (B) is titanium tetrabutoxide. 16 The precipitant is lithium alkyl, Grignard reagent,
7. The method according to any one of claims 1 to 6, wherein the compound is a dialkylmagnesium compound or a dialkylzinc compound. 17. The method according to claim 16, wherein the precipitant is a dialkylmagnesium compound.