DE2555165A1 - IMPROVED POLYMERIZATION CATALYSTS AND THEIR MANUFACTURING - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAlR

PATENT LAWYERS? ζ S 5 1 R 5

8 MUNICH 86, POST BOX 86 02 45 i ^{JJJ IUlJ}

Attorney file 26 599
Be / Ro

iüoa JJenryo Kogyo K.IC Tokyo / Japan

"Improved Polymerization Catalysts and Their Manufacture"

This invention relates to the improvement of a catalyst component (hereinafter referred to as the catalyst component) used in the polymerization of alpha-olefins Use finds, in particular, a process for the preparation of a catalyst component with excellent cataly-

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• (089) 988272 8 Munich 80, Mauerkircherstraße45 Banks: Bavarian Agreements Munich 453100

98 το 43 telegrams: BERGSTAPFPATENT Munich Hypo-Bank Munich 389 2623

983310 TELEX: 0524560 BERG d Postscheck Munich 65343-808

table properties, making "in the stereoregular Polymerization of alpha-olefins, as in particular of Propylene, not only improves stereoregularity, but the rate of polymerization is also markedly increased.

In a process for producing a crystalline polyolefin on an industrial scale, it has been proposed so far, to use a polymerization catalyst which contains in combination a catalyst component which is a Low valence transition metal halide and a promoter component composed of an organic metal compound, includes. In particular, titanium trichloride has heretofore been used as a transition metal halide.

One known method of making titanium trichloride is to mix titanium tetrachloride with aluminum metal reduced at high temperatures and then brings the product to activation for grinding. The on this A prepared catalyst component is usually referred to as AA grade titanium trichloride and contains except Titanium trichloride aluminum chloride in eutectic form, but has the disadvantage that when used as a polymerization catalyst the rate of polymerization and stereoregularity are unsatisfactory, and that in the commercial Scope required a large amount of expensive catalyst is while at the same time incurring great costs to the

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to treat non-crystalline polymers formed as by-products. Furthermore, through this process obtained catalyst component a broad particle size distribution and using this catalyst component polymerized polymer also has a broad particle size distribution, making different Difficulties arise in handling the polymer powder.

Another known method of making a titanium trichloride compound is that of titanium tetrachloride reduced by diethylaluminum chloride, the latter being used in proportions which are equimolar or less than the moles of titanium atom present, at lower temperatures, such as this, for example in Japanese Patent Publications Kr. 10415/1971, 21575/1972 and II8O7 / I972. This method has the advantage that a catalytic component with a relatively uniform particle size can be obtained, but that on the other hand, the titanium trichloride obtained by this process is brown beta-titanium trichloride, its Polymerization capacity is very low. It is therefore necessary to combine heat activation treatment to subdue to convert them to violet titanium trichloride. In this case, however, the rate of polymerization and stereoregularity are when used as Polymerization catalyst of the above-described titanium

80982S / DSÖ3 " ⁴ "

trichloride quality AA not superior.

As another process for the production of titanium trichloride has been proposed to provide a catalyst component having a relatively high rate of polymerization, high stereoregularity and to achieve excellent particle size distribution, titanium tetrachloride using diethylaluminum chloride at low temperature to obtain a beta-type titanium trichloride, and then this Treat compound with an ether compound and titanium tetrachloride to turn it into a purple reduced pesticide of the delta type as described in Japanese Patent Application (OPI) Kr. 34478 / 19.72. However, this method requires a large amount of titanium tetrachloride and a high concentration of titanium tetrachloride in an inert extender, for example 15, preferably 30 to 40 volume ^. It was determined, that in the case of treatment with a titanium tetrachloride solution with a concentration of 40 volume ^, a catalyst component obtained for polymerization with a relatively high polymerization activity and stereoregularity while in the case of treatment with a titanium tetrachloride solution at a concentration of 10 Volum-Jo a catalyst component with unsatisfactory Properties is obtained. It has also been found that it is difficult to obtain a Catalyst component with an essentially good par

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to get article size distribution. That is, in the event treatment with high concentration titanium tetrachloride solution produces a catalyst with a uniform particle size distribution tends to break into fine particles with a wide particle size distribution.

According to the present invention, it has been found that a catalyst component having excellent catalytic Properties can be obtained by using titanium tetrachloride with a mixture of dialkyl aluminum halide and reduced alkylaluminum dihalide, the dialkylaluminum halide being used in a proportion which is equal to or greater than the moles of titanium tetrachloride present.

Accordingly, the invention provides a process for preparing a catalyst component for polymerization of alpha-olefins, including titanium tetrachloride with dialkyl aluminum monohalide and monoalkylaluminum dihalide, wherein the hydroxyalkylaluminum monohalide is at least equimolar proportion compared to the titanium tetrachloride is present, and that this compound is formed of a purple reduced solid.

According to a further embodiment, the subject is ■ reduced solid obtained by the method described above in a heat treatment.

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In a further embodiment, the reduced solid obtained by the first stage is treated with a Lewis base and then with a hydrocarbon solution of Titanium tetrachloride

Useful examples of dialkyl aluminum monohalide used for reducing titanium tetrachloride in the inventive Methods that can be used include dimethyl aluminum chloride, Diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide and like that. Diethyl aluminum chloride is preferred.

Useful examples of monoalkylaluminum dihalides, which can be used in conjunction with the dialkyl aluminum monohalide in the process of this invention Methyl aluminum dichloride, ethyl aluminum dichloride, butyl aluminum dichloride, Ethyl aluminum dibromide and ethyl aluminum iodide. Ethyl aluminum dichloride is preferred.

ET is now only for explanation and without limitation the present invention using the combined use of ethylaluminum dichloride and diethylaluminum chloride described.

As stated above, one method is to reduce Titanium tetrachloride known to the person skilled in the art with the aid of diethylaluminum chloride. This reaction proceeds according to the following Equations from:

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+ 0.5At ₂ AlGl - »TiCl ^ + 0.5 AlGl ₅ + It + 1.0At ₂ AlCl -3> TiGl ₅ + ItAlCl ₂ + It

From these equations it can be seen that the relationship Diethyl aluminum chloride to titanium tetrachloride usually 0.5i1 to 1.0: 1. It is generally known, that the compound formed by this reaction, i.e., ethylaluminum dichloride, is used for the polymerization reaction is harmful material and efforts have therefore been made to limit this as far as possible after the reduction reaction remove. However, it has been found that a purple reduced solid is obtained when titanium tetrachloride is used by means of diethyl aluminum chloride and ethyl aluminum dichloride in an appropriate amount in a proportion of 1 mole or more of diethyl aluminum chloride to 1 mole Titanium tetrachloride, in particular reduced in a proportion of 0.3 to 1.2 mol per 1 mol of titanium tetrachloride. This shows reduced solids when it is used as a catalyst component for the polymerization of alpha-olefins, one has a higher polymerization activity than a catalyst component obtained by reducing titanium tetrachloric obtained using diethylaluminum chloride alone. It was further found that a catalyst component (heat-treated solid) with improved Polymerization activity and stereoregularity, the least corresponds to that of the titanium trichloride launched on the market, as well as with a noticeably improved particle size

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Uniformity of size can be achieved if the previously reduced solid is subjected to a heat treatment. In addition, it was found that a catalyst component with further improved polymerization activity, Stereoregularity and particle size uniformity is achieved when using the reduced solid a Lewis base like ether and then with a hydrocarbon solution treated by titanium tetrachloride.

One object of the method of this invention is to that if you mix titanium tetrachloride with diethylaluminum chloride and ethylaluminum dichloride in a suitable Amount in a ratio of 1 mole or more of diethylaluminum chloride to 1 mole of titanium tetrachloride, in particular im Reduced ratio of 0.3 to 1.2 mol to 1 mol of titanium tetrachloride, a purple reduced solid is obtained. This fact is very surprising in view of the prior art method in which one does not Ä "t hylaluminiumdi chloride, but exclusively diethylaluminum chloride used. The X-ray diffraction spectrum shows that in the case of a brown reduced solid, obtained by the prior art method, the peaks at 2Θ = 42.2 ° (beta-type crystal) are considerably larger than the peak at 2 © = 51.3 ° (gamma-type crystal), while in the case of one after the present invention obtained violet reduced dye the peak at 2Θ = 42.2 ° very small and the

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" ⁹ " 2555163

Peak at 2Θ = 51, f is large.

Another object of the present invention is that the preparation reduces the above-described Contains solid. If titanium tetrachloride is reduced in equimolar amounts using diethylaluminum chloride, becomes titanium trichloride and ethylaluminum dichloride in equimolar amounts Quantities formed as a by-product. This by-product is easily soluble in solvents, but even so if the reduced solid is sufficiently washed with a solvent after the reduction reaction, one remains significant amount of aluminum dichloride in the solid. It is believed that the aluminum dichloride is a component is present to form a reduced solid with some cohesive strength, making it difficult is to remove the compound by washing. If you have a reducing agent, you can use the ethylaluminum dichloride admits, used for the reduction of titanium tetrachloride by the process of the present invention, is the content of the aluminum compound in the reduced solid is greater than in the reduced solid which is obtained after the State of the art obtained in which no ethylaluminum dichloride is added. This observed in the method of the invention Tendency is of interest in view of the fact that when diethylaluminum chloride is used alone as a reducing agent, the aluminum dichloride content in the reduced solid appears to decrease,

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when a diethyl aluminum chloride to titanium tetrachloride im Ratio of 1 or more is present. Examples of the analytical composition of the reduced solids are indicated in the table below:

Reducing agent Al / Ti ratio Al / Ti ratio

in the reduction in the reduced pesticide

Ät ₂ Αΐσι 5AtAlCl ₂ 1 0.35 OAtAlCl ₂ 1.5 0.22 5AtAlCl ₂ 2 0.26 2.5 0.18 At ₂ AlCl + O, 1.5 0.56 At ₂ AlCl + 1 1 2 0.56 At ₂ AlCl + 1, 2.5 0.62

The above-described reduced solid of the invention is characterized by having a higher polymerization activity when used as a catalyst component for the polymerization has compared to a reduced Solid obtained using only diethylaluminum chloride according to the previous process receives. That is, the stereoregularity and the effectiveness as polymerization properties are lower when using an organoaluminum compound as a cocatalyst adds to a reduced solid by the previous process, and that the polymerization of alpha-olefins, for example only half as fast as with titanium trichloride the commercially available quality AA.

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ϊ 'G-egensatz to have the reduced solid of the pre-' * 'lying invention is substantially the same as the polymerization litantrichlorid the quality of AA.

When the reduced solid one after the first Process of the present invention involves a heat treatment in an inert solvent such as a hydrocarbon is subjected, a catalyst component (heat-treated solid) is thereby obtained with both excellent polymerization activity and stereoregularity. This catalyst component is the im Commercially available AA grade titanium trichloride in superior to particle size uniformity and has polymerization activity and stereoregularity at least that of titanium trichloride corresponds to quality AA.

If you have a reduced solid that can be obtained by reducing titanium tetrachloride using only it obtained from diethylaluminum chloride, subjected to a similar heat treatment, both the polymerization activity and stereoregularity are lower than those of im Commercially available AA grade litanthine trichloride.

When the heat-treated solid obtained by the process of the present invention is used as a catalyst component is used, one obtains a polymerization activity and stereoregularity which is at least

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use of titanium trichloride, which is commonly available commercially corresponds to quality AA, the polymer having a narrower particle size distribution.

According to a further object of the invention, a
Catalyst component, their polymerization behavior
is markedly improved, can be obtained by subjecting the first catalyst component of the invention to a further effective aftertreatment. This means that the reduced pesticide obtained by the first process of the invention is treated with a Lewis Ease such as ether and then with a solution of titanium tetrachloride, whereby a catalyst component having a higher polymerization activity and
Stereoregularity is obtained as a catalyst component in which titanium tetrachloride is reduced using only diethylaluminum chloride and the resulting reduced pesticide is subjected to a similar post-treatment.

Another object of the present invention is the concentration effect of the treatment step with titanium tetrachloride. A catalyst component with excellent polymerization activity and stereoregularity is obtained, if the reduced solid obtained after the first decay of the present invention with treated with a titanium tetrachloride solution, which has a lower concentration than in the case of one after the previous one

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Reduced pesticide obtained method. In the treatment with a solution of titanium tetrachloride by the method of the prior art is a titanium tetrachloride concentration of 15 ^ Volurn- or higher, in particular 30 to 40 ^c p required. It can therefore be obtained a catalyst component with a considerably improved activity by using a titanium tetrachloride concentration of 40 yb by volume even in the post-treatment of a reduced solid obtained by reducing titanium tetrachloride using only diethylaluminum chloride by the previous method, wherein however, the use of a titanium tetrachloride solution with a lower concentration of, for example, 10 volumes, produces a catalyst component with unsatisfactory properties. On the other hand, the reduced solid obtained by the first process of the present invention is capable of providing a catalyst component having the same polymerization activity as that obtained by treating with titanium tetrachloride solution having a concentration of 40% by volume by the previous process obtained, even if one works with a titanium tetrachloride solution with a lower concentration, for example 5 Volum- ^, provided that an aftertreatment with a Lewis base, such as ether compounds, is carried out. In addition, if a treatment is carried out using a titanium tetrachloride solution having a concentration of 10 volume $, a catalyst can

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-H-

Sator component with a higher polymerization activity can be obtained as if the treatment using a titanium tetrachloride solution with a concentration of 40 volume-> i according to the state of the art .

Because it is now possible to use a dilute solution of titanium tetrachloride in the method of this invention, not only does this have the advantage of high activity without using a large amount of the expensive reagent -can be obtained, but that you also have a catalyst component obtained, which has an excellent particle property. As can be seen from the examples and comparative examples, contains a catalyst component in the final state a considerable amount of fine particles, if the reduced pesticide with an ether compound and then treated with titanium tetrachloride. The use of such a catalyst component is for the polymerization is disadvantageous because it creates a polymer powder that contains a large amount of fine particles, will be produced. However, the method of the present invention has an advantage that the fine powder content in the catalyst component can be reduced by lowering the concentration of titanium tetrachloride.

The reducing reaction of the invention is carried out in US Pat Way that you can titanium tetrachloride with a reducing

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agent which is a monoalkylaluminium adihalide and Contains dialkylaluminum monohalide, brings into contact, "for example ethylaluminum dichloride and diethylaluminum chloride in an inert diluent. In particular, the reducing agent which is used to reduce ' ! Eitantetrachlorid is used, diethyl aluminum chloride in an equimolar or greater proportion to titanium tetrachloride and ethylaluminum dichloride in a suitable one Proportion of. If diethyl aluminum chloride in a lower is used as an equimolar proportion to titanium tetrachloride, show the reduced solid obtained, the heat-treated Solid and the ether and titanium tetrachloride treated solid overall unfavorable properties. The amount of ethyl aluminum dichloride used is preferably in the range of 0.3 to 1.2 moles per mole of titanium tetrachloride.

Aliphatic hydrocarbons having 4 to 12 carbon atoms or alicyclic hydrocarbons which are essentially free of aromatic hydrocarbons can be used as inert extender or diluent. The temperature of the reduction reaction is be set relatively important for the properties of the final product and it should at -50 to +30 ⁰ C. The reaction is initiated by bringing titanium tetrachloride into contact with a reducing agent, with stirring, and a reduced solid is then formed which is contained in the

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erten diluent is insoluble, precipitated. The reaction is usually carried out, for example, by adding dropwise either the solution of titanium tetrachloride or the solution of the reducing agent, gradually adding to the other, or vice versa. The total time required for mixing the solutions is 1 hour or more, preferably 3 hours or more, and during the same time, the reaction system should be kept at the above-described temperature. After the solutions have been both completely mixed and kept at the same temperature for at least 30 minutes, preferably 1 hour or more, the temperature is gradually increased and the system is kept at a constant temperature in the range from 20 to 120 ^° C. for 15 minutes or more , preferably 60 to 100 ⁰ C. The reduced Peststoff obtained in this manner should be sufficiently washed with fresh solvent.

The heat treatment of the reduced solid is optionally in an inert medium at a temperature of 120 to 18O ⁰ C for 30 minutes or more, preferably 1 to 3 hours is performed. In this case, aliphatic hydrocarbons or alicyclic hydrocarbons which are substantially free from aromatic hydrocarbons are used. For example, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, and the like can be used.

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In the event that the reduced solid with a Lewis base treated, subjected to the reduced solid solvent extraction treatment in the presence the Lewis base. Ethers, thioethers, thiols, organic phosphorus-containing ones can be used as Lewis bases Compounds, organic nitrogen-containing compounds, Ketones and esters. Useful examples of ethers are: diethyl ether, diisopropyl ether, di-n-butyl ether, Μι sobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, di-2-ethylheptyl ether, Allyl ethyl ether, allyl butyl ether, diphenyl ether, Annisol, phenylethyl ether, ghloranisole, bromanisole and dirnethoxybenzene. As thioethers, for example usable: diethyl thioether, di-n-propylthioether, Dicyclohexylthioether, diphenylthioether, ditolylthioether, ethylphenylthioether, propylphenylthioether and diallylthioether. Examples of organic phosphorus-containing compounds are tri-n-butylphosphine, triphenylphosphine, Triethyl phosphite and iributyl phosphite. Examples of organic nitrogen-containing compounds useful here are, are diethylamine, triethylamine, n-propylamine, Di-n-propylamine, tri-n-propylamine, aniline and dimethylaniline. In particular, ethers, preferably with 4 to 16 carbon atoms, are suitable. The extraction process can be carried out by any of the conventionally used methods, such as sufficient Stirring the reduced solid with an ether compound in an inert medium with separation

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into a liquid and solid phase. The solvents used in the reduction reaction can also be used as the medium. The extraction usually leads to 5 minutes or more, preferably 30 minutes to 2 hours at a constant temperature of 0-80 ⁰ C. The amount of the Lewis base used is in the range of 0.1 to 2.5 mol, preferably 0.8 to 1.0 mol per 1 mol of titanium atom.

The solid treated with the Lewis base described above is then subjected to treatment with a titanium tetrachloride solution which should have a concentration of 5 Yolum-Jö or more. When the concentration is less than 5 volume ^, one obtains only an insufficient one Polymerization activity and unsatisfactory stereoregularity of the polymerization product, while if the concentration of titanium tetrachloride is increased, good results are obtained in terms of the polymerisation activity and stereoregularity of the product, however, as described above, there is a tendency that the particle size distribution is caused by an increase is expanded by fine particles. A titanium tetrachloride concentration of 5 to 20 volumes by volume is therefore preferred. As the hydrocarbon solvent used in this case pentane, hexane, heptane, octane, cyclohexane, cyclopentane and the like can be given. the Temperature during treatment with a titanium tetra-

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Chloride solution is in the range from -30 to +100 ⁰ G, preferably from 40-80 ⁰ C. This titanium tetrachloride treatment can be carried out in about 30 minutes, but should last 1 to 3 hours in order to achieve good results with high reproducibility. After the titanium tetrachloride treatment, the obtained catalyst component should be sufficiently washed with fresh solvent because the polymerization will be adversely affected if a large amount of titanium tetrachloride remains.

The catalyst component obtained in this way can be used for polymerization together with a cocatalyst component be used. Organometallic compounds are used as cocatalysts used by elements of group G I, II and III of the periodic table. In particular, are preferred Organoaluminum compounds are used, and in particular triethylaluminium and diethylaluminum are Chloride suitable for the polymerization of propylene. All polymerization processes known to the person skilled in the art can be used. For example, a liquid monomer can be used as the polymerization medium in an economical process without the use of a polymerization diluent or, similarly, it can be a gaseous monomer be used.

example 1

150 ml of purified heptane and 34.8 ml! Ditantetra-

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chloride in a flask with a capacity of 500 ml, which is equipped with a stirrer and kept at ^{0 0} C in a bath. 40 ml of diethylaluminum chloride (equimolar to titanium tetrachloride) and 16.5 ml of ethylaluminum dichloride (0.5 mol / mol of titanium tetrachloride) are dissolved in 160 ml of heptane and added dropwise from a dropping funnel. The dropping is continued for about 3 hours and during the same time the reaction system is kept at 0 ° C. After the dropwise addition, the reaction mixture is gradually heated to 65 ° C. for 1 hour while stirring. The reaction is continued at the same temperature for 1 hour. After the reaction, the reaction mixture is allowed to stand to separate. A solid forms and the supernatant liquid and the solid are washed three times with 150 ml of purified heptane, then dried at 65 ° C. for 30 minutes under reduced pressure. The reduced solid has a red-violet color} its X-ray diffraction spectrum shows that the tip at 2Θ = 42.4 ° (crystal of the beta type) is considerably narrower than the tip at 2Θ = 51.3 ° (crystal of the delta type ). The proportion of fine particles of 5 µm or less in the reduced solid is t $ or less.

100 mg of the reduced solid obtained in this way are added in a 1000 ml autoclave, to which 180 mg diethylaluminum chloride as cocatalyst, 600 ml hydrogen (im Standard condition) as a molecular weight regulator and 800 ml

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adding liquid propylene. The polymerization is carried out at 68 ° C. for 1 hour and the unreacted propylene is subjected to the Schneilabtrieb, whereby 96 g of polypropylene powder are obtained. The polymer yield per 1 g of reduced solids (hereinafter referred to as "catalyst efficiency E") was 960. The melt flow rate according to ASTM D 1238 (MFR) of this polymer was 6.0. The heptane-insoluble content (HI) of the polymer was 70.7 %, which was measured by extracting with boiling heptane for 5 hours using a Soxhlet extractor.

20 g of the reduced solid described above are suspended in 200 ml of purified heptane and the suspension is subjected to the heat treatment at 150 ° C. for 2 hours. The solid is then separated off, dried at 65 ^° C. for 30 minutes under reduced pressure, and a heat-treated solid is obtained. The proportion of fine particles of 5 µm or less in this heat-treated solid is $ 5. Using this heat-treated solid, a polymerization test is carried out under the same conditions as above and a polymer yield (E) per 1 g of heat-treated solid of 960, an MFR and an HI of the polymer formed of 50 and 93 »7 $, respectively.

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Comparative example 1

The procedure of Example 1 is repeated, except that no ethylaluminum dichloride but only diethylaluminum chloride is used during the reduction. The color of the reduced solid formed by the reduction is brown, and its X-ray diffraction spectrum shows that the peak at 20 = 42.4 ° is larger than the peak at 20 = 51.3 · The proportion of fine particles is 5 / µm or less 1 fo or less.

A polymerization study is carried out using this reduced solid under the same conditions as in Example 1 and obtains the following results:

E = 520, HI = 68.3 f ₀ , MFR = 6.5

If this reduced solid is heat-treated in a manner analogous to Example 1, the color changes from brown to purple. The proportion of fine particles of 5 µm or less in the heat-treated solid particles is $ 5. If a polymerization study is carried out using this solid in a similar manner Carry out the same procedure as in Example 1, the following results are obtained:

E = 750, HI = 92.5 $, MFR = 5.0

Comparative example 2

Using AA grade titanium trichloride manufactured by Toyo Stauffer & Co, a polymeric 609828/0903 ~ ²³ ~ is carried out

sation investigation under the same conditions as in Example 1 and get the following results:

E = 850, HI = 93.3 #, MFE = 4.0

The proportion of fine particles of 5 µm or less in these AA grade lithium trichloride particles is 12 fo.

Examples 2 and 3

The procedure of Example 1 is repeated except that the ratio of ethylaluminum dichloride used changes to titanium tetrachloride as a reducing agent. The amount of diethyl aluminum chloride is the same as in Example 1. The results of a polymerization study of the reduced solid and the heat-treated Solids are given in Table I below.

Table I.

Example Kr, 2 2

ÄtgAlCl / liCl. Molar ratio 1.0 1.0

EtAlCl ₂ / _{TiCl 4} molar ratio 0.3 1.2

Proportion of fine particles of 5 / µm

or less in the reduced '11

Solid (#)

Polymerization study results of the reduced solid

Proportion of fine particles of 5 / µm or less in the heat-treated '
delten solid (#)

Polymerization study results of the heat-treated solid

E.
HI 722
73.9 840
78.0 5 5 E.
HI 664
92.9 800
93.5

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Comparative "examples 3, 4 and 5

The procedure of Comparative Example 1 is repeated, except for the ratio of diethylaluminum chloride used changes to titanium tetrachloride as a reducing agent. The results are given in Table II. This table shows that the use of the reducing agent in an excess amount over titanium tetra chlcri d brings no advantages.

Table II Comparative Example Ur ₀ g 4 5

Molar ratio 0.5 1.5 2.0 ₂₄ Molar ratio 0 0 0

Proportion of particles of 5 / µm or

less in the reducing ' 112

th solid (#)

Polymerization study results

of the reduced solid E 94 580 720

HI 77.4 65.4 62.1

Particle fraction of 5 / µm. or

less in the heat

traded pesticide (56) - 6 6

Polymerization study results

of heat treated solid E - 460 580

HI - 90.5 90.1

Comparative Examples 6 and 7

The procedure of Example 1 was repeated except that the proportion of diethyl aluminum chloride to titanium tetrachloride was adjusted to 1. The results are in the table III stated. It can be seen from this table that only poor results are obtained when the amount of diethylaluminum chloride is kept small, even if you use ethyl

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aluminum dichloride is added.

Table III Comparative Example No. ₀

. Color ratio 0 0.5

g ^ molar ratio 1.0 0.5

Particle content of 5 µm or less

in the reduced plague

fabric (fo) 11

Polymerization study results

of the reduced solid E 150 550

EI 79.0 77.0

Proportion of particles of 5 / µm or less in the reduced solid '

Polymerization study results

of the heat-treated solid E 160 500

HI 90.2 86.3

Examples 4 and 5

The procedure of Example 1 is repeated, except that the amount of diethylaluminum chloride used is added increased more than 1 mole to 1 mole of titanium tetra-chloride. the The amount of ethyl aluminum dichloride is kept constant (0.5 mol to titanium tetrachloride). The results are in the table

IY specified.

example Ήτ. Table IV 4 5

Et ₂ AlCl / _{TiCl 4} molar ratio 1.25 1.5

EtAlCl ₂ / TiCl, molar ratio 0.5 0.5

Particle content of 5 µm or less

in the reduced solid ($) 1 1

Polymerization study results of the reduced solid E 848 841

HI 61.3 69.2

Particle content of 5 µm or less

in the heat treated solid ($) 5 6

Polymerization test results E 706 762

of the heat treated solid HI 92.4 90.7

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Example 6

20 g of the reduced solid obtained in Example 1 are suspended in 200 ml of concentrated heptane and mixed 20 ml diisoamyl ether (equimolar to the titanium in the reduced Solid) and reacts at 35 ° C. for 1 hour. After the reaction, the reaction product is washed twice 150 ml each of purified heptane. Then you are suspended the product in turn in a heptane solution containing 40 volume $ titanium tetrachloride, and sets at 65 ° C for 2 hours around. After the reaction, the reaction product is washed three times with 150 ml of purified heptane each time and dried 65 ° C for 30 minutes under reduced pressure.

100 mg of the catalyst solid obtained above are placed in a 1000 ml autoclave, in which 180 mg of diethylaluminum chloride are placed as a cocatalyst, 600 ml of hydrogen (standard state) as a molecular weight regulator and 800 ml introduces liquid propylene. The polymerization is carried out at 68 ° C. for 30 minutes and the unreacted material is removed Propylene by rapid stripping, giving 196 g of polypropylene powder. The polymer yield (E) per 1 g of catalyst solids is 1960, the MFR is $ 4.5 and the HI is $ 97.0. If you look at the particle size distribution the solid catalyst particle measures, the proportion of fine particles of 5 µm or less is 12 $.

Comparative example 8

The reduced solid obtained in Comparative Example 1

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substance is subjected to a treatment with diisoamyl ether and then with a titanium tetrachloride solution under the same conditions as in Example 6 and obtain a catalyst solid, with which the following results can be obtained in a polymerisation study:

B = 1410, HI = 97.4 $, MFE. = 4.0

If the particle size distribution of the catalyst solid particles used is measured, the proportion of fine particles of 5 μm or less reaches 36 <fo.

Comparison example 9

Made using "AA grade titanium trichloride." from Toyo Stauffer & Go., a polymerization study similar to that in Example 6 is carried out and gets the following results:

E = 430, HI = 93.1 #, MFE = 4.7

Examples 7 »8, 9 and 10

The procedure of Example 6 is repeated except that the concentration of titanium tetrachloride is increased to 40.15 and $ 5 volume during treatment with titanium tetrachloride changes. The results are compared with those of Example 6 in Table V.

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Table V Examples No. 6 7 8 9 10

Titanium tetrachloride

Vol.-5b 40 40 15 15 15

E 1960 1620 1990 1650 1360

HI 97.0 97.6 97.6 97.2 95.4

MFR 4.5 5.1 6.0 5.8 4.6

io to particles with

5 / um or less 12 11 6 5 5

This table shows that even when using titanium tetrachloride in a low concentration, the polymerization activity and the HI are not lowered, and that the proportion decreases in fine particles. Therefore, good results can be obtained by the method of the present invention will.

Comparison examples 10, 11, 12 and 15

The procedure of Comparative Example 8 is repeated except that the concentration of titanium tetrachloride is determined 40, 15 and 5 Vo1- $ during treatment with titanium tetrachlaid changes. The results are given in Table VI with those of Comparative Examples 8 and 9 »

Table VI _G

Comparative examples ITr. 8 K) JJ 12 quality AA

Titanium Tetrachloride Vol- $ 40 40 15 5 -

E 1410 1210 1160 950 430

HI 98.1 96.9 95.5 97.4 93.1

MPR 4.0 4.8 6.1 5.0 4.7

io of particles of 5 / around 36 34 29 30 12 or less'

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In the table it can be seen that after the procedure according to the prior art, i.e. according to a process in which ice in ethylaluminum dichloride is added during the reduction, the activity is low when the concentration of titanium tetrachloride is 15 volumes or less.

Examples 11, 12, 13, H and 15

The procedure of Example 6 is repeated except that the amount of ethylaluminum dichloride used is reduced is changed by titanium tetrachloride. The molar ratio from diethylaluminum chloride to titanium tetrachloride is kept at 1. The results are given in Table VII.

Table VII Example no. 11 12th 13th 14th 15th Conditions of manufacture
of the reduced solid Et ₂ AlCl / TiCl, molar ratio 1.0 1.0 1.0 1.0 1.0 EtAlClp / TiCl. Molar ratio 0.3 0.5 0.75 1.0 1.2 Polymerization Investigation
Results
E. 1510 1840 1620 1720 1680 HI 97.2 97.9 93.0 97.4 97.5 MFR 4.9 6.3 2.5 5.2 4.9

fo the particle of / around 5 or

less ⁷ 16 12 12 14 14

Comparative Examples 14t 15, 16, 17 and 18

The procedure of Example 8 is repeated except that only diethylaluminum chloride is used for the reduction

^ Comparative -30-

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and its proportion changes to titanium tetrachloride. The results are given in Table VIII. this table
shows that the use of diethylaluminum chloride as a reducing agent is ineffective even if it is used
used in excess.

Table VIII Comparative example CTr. 14 15 16 17 18

Conditions of manufacture
of the reduced pesticide

Et ₂ AlCl / TiCl ₄ molar ratio 0.5 0.75 1.0 1.5 2.0 ItAlCl ₂ ZTiCl, molar ratio 0 0 0 0 0

Polymerization test results

E 90 350 1390 1280 HOO

HI 88.0 94.0 97.9 96.8 96.5

MPR 2.8 4.0 3.9 7.1 6.4

fo the particle of 5 / µm or

less ' 4 8 35 29 39

Examples 16 and 17

The procedure of Example 6 is repeated except that
the reduced ones prepared in Examples 4 and 5
Pesticides are used as reduced pesticides,
and that they are subjected to ether and titanium tetrachloride treatment. The results are given in Table IX.

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Table IX Example Ir, 16 17th Conditions of manufacture
of the reduced solid ÄtgAlCl / TiCl, molar ratio
EtAlCl ₂ / TiCl. Molar ratio 1.25
0.5 1.5
0.5 Polymerization Investigation
Results
E. 1980 1927 HI 97.6 99.2 MFR 4.0 3.5 fo particles of 5 µm or less 10 11 Comparative examples 19, 20 and 21

The procedure of Example 6 is repeated except that a reduced solid is used, which is thereby obtained prepares that the reduction while adjusting the molar ratio of diethylaluminum chloride to Sets titanium tetrachloride to 1.0 or less, and then follows Xther and titanium tetrachloride treatment leaves. The results are given in Table X.

It can be seen from this table that only poor results are obtained when the amount of diethylaluminum chloride is low, even if ethyl aluminum

dichloride. is present and you get the reduced solid subjected to an ether and titanium tetrachloride treatment.

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Table X Example no.19 20 21

Conditions for making the reduced solid

Molar ratio molar ratio

Polymerization study results

HI
MPR
° / o particles of 5 / µm or less

O 0.5 3 0.75 1.0 0.5 9 0.75 520 210 510 93.9 82, 92.4 4.8 3, 4.7 6th 8th 9

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Claims (12)

Patent claims: U Process for the production of a catalyst component for; Polymerization of alpha-olefins, thereby gel I i indicates that you can use titanium tetrachloride a mixture of dialkyl aluminum halide and alkyl aluminum; treated sodium dihalide, the dialkylaluminum halide in the mixture is used in a proportion which is at least equimolar to the titanium tetrachloride present, and that these compounds are reacted to form a reduced purple pesticide. 2. The method according to Anspru chi, characterized to subject the solid thus obtained to the heat treatment. 3. The method according to claim 1, characterized that the so reduced pesticide with a. lew.is base and then treated with a hydrocarbon solution of titanium tetrachloride. 4. The method according to any one of the preceding claims, characterized in that one diethyl aluminum chloride is used as dialkyl aluminum halide and ethyl aluminum dichloride is used as alkyl aluminum dihalide . 5. The method according to one of the preceding claims, -34-609826 / 09 0 3 characterized in that the alkylaluminum dihalide in a ratio of 0.3 to 1.2 moles per mole of titanium tetrachloride are used. 6. The method that is carried out according to any one of the preceding claims, characterized in that the reduction reaction at a temperature of -50 to +30 ⁰ C. 7. The method according to one of claims 3 - 6, characterized in that one effects the heat treatment at a temperature in the range of 20 to 12O ⁰ C. 8. Catalyst component, provided it is produced by a method according to any one of claims 1-7 » 9. Process for the polymerization of an alpha-olefin, characterized in that an organoaluminum compound is converted into a catalyst component added, which are prepared by the process of claims to 7, and that then the alpha-olefin is a Polymerization reaction in the presence of the catalyst component and the organoaluminum component subjects α 10. Process for the preparation of a catalyst component, essentially as described in the examples 609826/0903 11. Catalyst component, essentially like, »in the Examples described. 12. Process for the polymerization of alpha-olefin, im essentially as described in the examples. 609826/0903 ORiGiNAL INSPECTED