DD160454A5 - METHOD FOR PRODUCING A CATALYST VEHICLE - Google Patents

Abstract

The invention relates to a process for the preparation of a catalyst carrier for use in the alpha olefin polymerization. The object of the invention is to produce the catalyst in an economical manner while reducing energy consumption and environmental pollution, thereby obtaining a catalyst with which polyolefins are obtained in good yield and high purity. According to the invention, a first titanium-free, particulate substance suitable for use in the alphaolefin polymerization is permeated with a second solid to form a titanium-free, particulate carrier mixture, this second solid being different from said first particulate substance, but substantially having the same structural configuration , After this penetration, the particulate carrier mixture thus obtained becomes an organic electron donor compound. wherein at least a portion of said electron donor compound reacts with said second solid at least on the surface of said particulate carrier mixture to thereby produce a titanium-free, solid, particulate catalyst carrier having a lower specific surface area than said particulate carrier mixture.

Description

Process for the preparation of a catalyst support

Field of application of the invention

The invention "relates to a process for the preparation of a catalyst support.

In particular, the invention relates to a highly efficient Srägerkatalysator- for the production τοη polyolefins ·

Characteristic of the known technical solutions

Organometallic compounds have been used in combination with transition metal compounds to catalyze the production of high relative molecular weight ethylene and alpha olefin polymers and, in turn, to produce high steric regularity polymers employing them.

The basic catalysts used in these processes are formed by combining a transition metal salt with a metal alkyl or hydride. Often, titanium trichloride and an aluminum alkyl such as triethylaluminum or diethylaluminum chloride are used. However, such catalysts generally have low productivity and only form polymers of low steric regularity.

Isotactic polypropylene arises from a head-to-tail concatenation of the monomer units, as a result of which all asymmetric carbon atoms have the same configuration

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respectively. One of the measures of the percent isotactic isomer in the resulting polymer is the isotactic indes. Atactic polypropylene results from a random chain of monomer units. Isotactic polypropylene is an extremely useful industrial product of high tear strength, hardness, stiffness, impact resilience, transparency and improved surface gloss. Polypropylene is used industrially in the fields of injection molding as well as F.? one- and coarse foil as well as the filament and Paserhersteilung widest use. Technically useful polypropylene necessarily contains the sterically regular or isotactic isomer. Pur most applications, the polymer produced using such basic catalysts, must be extracted to ^

sr

To remove the atactic (not sterically regular) polymer and thus to increase the percentage of isotactic (sterically regular) polymer in the final product. In addition, the polymer produced by this process must also be doused to remove the catalyst excess. The additional production steps of polymer extraction and polymer deashing considerably increase the cost of the polymer produced with these basic catalysts *

The first improvement on these catalysts resulted from the use of mixed titanium trichloride and aluminum trichloride as a catalyst with an aluminum alkyl cocatalyst.

Later improvements focused on the supported catalysts. Many previous supported catalysts were based on the

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Reaction products τοη surface hydroxyl-containing Terbindungen with transition metal compounds. Examples of these include the reaction product of a transition metal compound with a bivalent metal hydroxychloride such as Mg (OH) Cl " -1,024,336, MG (OH) ₂ (BE-PS 726,832, 728,002 and 735,291), and with SiO ₂ , Al ₂ O ₃ , ZrO ₂ , .IiO ₂ and MgO. (GB ~ ^K 969 761; 969 767; 916 132 and 1038882).

Some later promoters have been based on the reaction products of transition metal-terminated magnesium alkoxides. Examples include the reaction product of a transition metal compound with 1Ig (OR) ρ (U.S.P.I. 3,644,318 and BB-PS Br. 737-778; 743,325 and 780,530).

Other supported catalysts were prepared on the basis of the reaction products of magnesium chloride with transition metal compounds. Lithanium compounds were synthesized with MgCl ₂ (U.S. Patent No. 3,642,746 and Belgian Patents No. 755,185; 744,221 and 747,846). Reaction brought.

Accelerated catalysts result from the addition of certain Lewis bases (electron donors) to the catalyst system. In certain situations, the electron donor has been combined with titanium trichloride during the preparation of the catalyst. Electron donors included the ethers, esters, amines, ketones, and gum aromatics. Even though the accelerated catalysts improved the isotactic index of the polymer, they were still generally unable to produce a polymer of such quality and quantity that the elimination of polymer extraction and polymer deashing

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would have allowed to eliminate the catalyst residue.

Recently, US Pat. No. 4,149,990 has described a catalyst component whose yield is so high that it appears to be sufficient to eliminate the steps of polymer deashing and polymer extraction. However, this catalyst has been produced in solution and thus requires a catalyst wash.

Object of the invention

The object of the invention is to provide a simple and economical process for the preparation of a new highly effective catalyst support for the production of polyolefins, with which the energy consumption and the pollution can be reduced.

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Explanation of the essence of the invention *. *

The. It is an object of the present invention to provide a catalyst support which, when used, forms a polymer having a sufficiently high isotacticity and a sufficiently low residue content, which in turn is able to be used without polymer extraction or polymer deashing.

The catalyst component of the present invention is prepared by permeating a particulate solid catalyst carrier with a second solid, with the. the former substance is essentially structural material. By reacting at least a portion of a first organic electron donor component with the second solid at least on the surface of the support (about its

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Reduce surface area), a particular particulate solid, titanium-free catalyst carrier is prepared. At least on the surface of the carrier, a polymerization-active transition metal compound - preferably a liquid Titaräumverbindung - attached, so as to produce a solid, titanium-containing catalyst component. Optionally, a second organic electron donor compound may be contacted with the support either prior to or simultaneously with the transition metal. Any combination of substances is preferably carried out in the absence of a solvent or an excess liquid reactant in a vibrating mill or ball mill. In this way, an improved, highly effective catalyst component with a low specific

Surface made of less than 1 m / g.

The catalyst component of the present invention overcomes a number of disadvantages of the known, state of the art catalysts. The catalyst component of the present invention not only overcomes disadvantages associated with the polymerization of alpha olefins to produce satisfactory industrial polymers, moreover, it produces a polymer of outstanding properties, and the catalyst component of the present invention exhibits outstanding properties it is produced by a process which not only offers substantial economic benefits _s but which additionally reduces the energy consumption and environmental pollution compared with the processes of the prior state of the art.

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The present invention provides a highly effective supported catalyst component for use in the polymerization of olefins, and in particular alpha olefins. Although the catalyst component has been used only in the homo-production of propylene, ethylene, and 1-butene, it may be assumed that the catalyst will also produce satisfactory homopolymers or copolymers of other alpha-olefins and lower molecular weight molecular weights.

It is believed that a supported catalyst component must be used to achieve the high productivity and steric regularity required to form a polymer of sufficiently high low isotacticity, which in turn is capable of no polymer extraction or Polymerentaärchung be used.

Thus, it is believed that a solid, isostructural solid, single carrier substantially capable of co-crystallizing with these titatium compounds will provide the best carrier. -

The leucule of the improved support forms a solid particulate material selected from the group consisting of HA and HIA salts as well as salts of the first transition series multivalent metals except copper. The magnesium and manganese salts represent the solid particulate carriers which are currently considered to be the most suitable. The magnesium and manganese dihalides, alkyloxides, aryllosides and combinations thereof have been found to be satisfactory in the art

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Preferred carrier bases are M (OR) X ₀ ", in which H is magnesium or manganese, E is an alkyl or .aryl, X is a halide and η is 0, 1 or 2 . Examples thereof include IgCl ₂ , IgBr ₂ , MgI ₂ Mg / Hg (OCH ₃ ) ₂ , Mg (OCH ₂ CH ₂ ) ₂ , Mg (OCgH ₅ ) _2, and combinations thereof. In the preferred embodiment, the magnesium dihalides, specifically magnesium aichloride, form the solid particulate carrier.

Magnesium dichloride is particularly preferred because of its high productivity as a part of catalyst components and the lower harmfulness of its residue in the polymer produced.

Due to the water and air reactivity of the catalyst component, it must be ensured that the water content of the solid particulate carrier is low enough so as not to interfere with the catalytic activity. For this reason, the magnesium dichloride used as support material in the preferred embodiment should be anhydrous. , · ...

Anhydrous magnesium dichloride is prepared by drying for 4 hours under an HCl blanket at 350 ^° C. or using other conventional means.

According to another characteristic feature of the present invention, a dehydrogenating, water-reacting agent is used to form, under the given reaction conditions, a readily volatile reaction product and a residue which does not adversely affect the alpha olefin polymerization. Such dehydrating agents include the silicone

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Tetrahalides, calcium carbide and calcium hydride. These agents may preferably be reacted by comminution in a vibrating mill or ball mill together with a hydrous, solid, particulate carrier material prior to the production of the catalyst component.

For this purpose, in the preferred embodiment, silicon tetrachloride has been used as the effective dehydrating agent. Silicone tetrachloride effectively dehydrated hydrous magnesium dichloride carrier and, surprisingly, had no apparent effect on the activity of the resulting catalyst. Preferred prices use only the amount of dehydrating agent which is sufficient. to react with the existing water. The molar ratio of silicon tetrachloride to water present in the carrier material should be about, Q-, 5: 1.

According to another characteristic feature of the present invention, the catalyst support which comprises a solid particulate carrier, at least the reaction product of a portion of the water therein and a dehydrating agent (preferably silicon tetrachloride) may be used in conjunction with any conventional means, to be attached to a polymerization-active transition metal compound. Preference is given to simultaneous comminution in the absence of a solvent. Other solvent methods have the disadvantage of the need for additional washing steps.

Bach this reaction, the resulting product as fe-

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particulate catalyst support material can be used in the production of any one of the catalyst components which normally require free particulate support and in particular anhydrous magnesium dichloride support.

Another important characteristic feature of the present invention is the use of a second - preferably also with octahedral titanium isostructural pesticide in addition to the solid particulate carrier material., ... Preferably, this second solid - differs from the solid particulate carrier material, but has essentially the same structure as this. This two-part pesticide is preferably selected from Group IIIA salts, especially the halides phosphorus or phosphorosyl trichloride. In the preferred method of the invention, this second -νοτ- lying Peststoff is ground simultaneously with the solid particulate carrier and, optionally, simultaneously with the dehydrogenated -Agens. At present, the aluminum trihalides and, in particular, aluminum trichloride are preferred as the second pesticide. The preferred molar ratio of carrier to second pest-preferably magnesium dichloride to aluminum trichloride-is about 8: 0.75 to 8: 1.5.

When starting with an anhydrous solid particulate carrier, the carrier and second pest (preferably magnesium dichloride and aluminum trichloride) are first contacted with each other, i. H. preferably crushed simultaneously in a rolling mill or ball mill or other similar apparatus with mixing action. In this case, an intimate admixture is formed at least from lagnesiumdichlorid and aluminum trichloride;

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If required, a solid solution of the formula MgClIp.C1 / K) AlCl-s can be prepared.

The aliiminium trichloride may act as an agglomerating agent because the specific surface area of the admixture or solid solution is rather small, generally about 4 x 6 m / g.

An additional characteristic feature of the present invention. Invention is the combination of a first organic electron donor with this carrier zwecks- generate an enhanced carrier * E _{3 y} is believed that at least a subset of said first electron donor reacts with the second substance, at least on the wearer Oberfläehe a Reaktxonsproduki; The formation of this product has a reduced specific surface area of the carrier, which may be due to blocking of the carrier's pores. " The resulting support generally has a specific surface area of less than about 2 m / g. When reacting the electron donor compound with the second solid, at least one component of this electron donor compound should preferably form a volatile by-product. Such a component will often be an alkyl group having less than 7 carbon atoms, preferably a methyl or ethyl group.

This electron donor compound can be selected from organic compounds having at least one oxygen, sulfur, nitrogen or phosphorus atom, that atom functioning as an electron donating atom. Examples of such electron donors are ethers, esters, ketones,

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Aldehydes, alcohols, carboxylic acids, phenols, thioethers, thioesters, thioketones, amines, amides, nitriles, isocyanates, phosphites and phosphines. The preferred electron donor compounds are the aromatic ethers and the esters, especially the alkylaryl ethers and the alkyl esters of carboxylic acids. This outstanding suitability is probably due to the existence of the pi-electrons of the aromatic ring adjacent to the electron donor atoms. The preferred molar ratio of solid particulate carrier to first electron donor compound in the preferred embodiment is about 10: 0.5 to 8: 2.0 with a very particularly preferred variant of about 8: 1 to 8:. 1.5 × * The molar ratio of first electron donor to the second Peststoff should be about 1: 1.

According to the current state of knowledge, methyl phenyl ether is the most effective first electron donor. This particular suitability may be due to the low steric hinderance of the methyl group as well as its inductive effect in addition to the advantage of the aromatic ring discussed above. In the reaction of methylthio phenyl ether with the second pesticide, further, a made up of highly volatile methane derivative. Nevertheless, whether or not there is complete clarity about their exact course, it is believed that the ether bond O-linkages react with the aluminum of the carrier or at least a portion thereof to produce a mixed phenoside and a volatile methyl chloride. See in this respect the relevant US-Application of serial no. 217 630 «. Although about the complete reaction and the structure of the carrier still present

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is not clear, it is considered possible that the reaction product of the methylphenyl ether and the aluminum trichloride reduces the specific surface area of the carrier by blocking the pores in the magnesium dichloride carrier.

The process of the present invention is primarily concerned with the initial co-comminution of the above-mentioned three components to obtain an improved titanium-free catalyst support. Although it is possible to blend all three components simultaneously, it has been found that better results with initial penetration of solid, particulate support material with second solid (preferably magnesium dichloride and aluminum trichloride) and subsequent addition and. Reacting the organic electron donor compound (preferably methyl phenyl ether) can be achieved. As already stated above, a dehydrogenating agent (preferably silicon tetrachloride) may be the solid particulate. Carrier _{% be} pre-mixed to react with this and remove any unwanted water.

In addition to the improved titanium-free catalyst support produced by the above process, the catalyst component of the present invention may contain a second organic electron donor compound. This electron donating compound can increase the steric regularity of the polymer by intertwining or reacting with the particulate carrier and thereby also bonding to the active transition metal compound, thereby forming a stable template upon which the polymer can form. This electron donor compound can be selected from the same group that makes up the primary

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Electronical Diver was selected; it can be the same or a difference connection. However, for the same reasons as already mentioned above, it is believed that the polyoxyethylene glycol ethers and alkyl esters of carboxylic acids (but especially the esters) give the best results. The most effective catalyst components have been prepared in particular by using ethyl benzoate as the catalyst second electron donor was used. "

The. preferred molar ratio of solid, particulate carrier material for the second electron donor is in -ß.er preferred embodiment of Jvlagnesiumdichlorid ethyl benzoate to about 8: 0.8 to 8. 1,2. The second electron donor compound should preferably be added in excess to the active transition metal compound The molar ratio of second electron donor compound to active transition metal compound in the most preferred variant of the preferred embodiment (benzyl benzoate to titanium tetrachloride) is about 1.6: 1 to 2; 4: 1. This second electron donor compound can be added and admixed to the support before, during, or after adding the active transition metal compound. In another embodiment, this second electron donor compound can be improved with the active transition metal compound prior to adding the resulting complex compound Carrier be combined.

The final component of the catalyst component of the present invention is an active, trivalent, tetravalent, or pentavalent transition metal compound of Group IVB-VIB metals, preferably of the formula M0_ (OR) X-n-p-D-m *.

•. "· - ·. -14.

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a group lYB-VIB metal of valence η = 3 «4 or preferred are the metals titanium, vanadium, chromium and zirconium. Currently, Titanium is the most preferable metal because of its outstanding productivity. O is oxygen; ρ is O or R is an alkyl, aryl or cycloalkyl group or a substituted derivative of these groups, where 0 <m · £ η. 2 represents any halide, that is a chloride, bromide, iodide or fluoride, although the chloride is preferred. The selection of a particular transition metal compound within the above formula will depend on the reaction conditions as well as the other ingredients present in the catalyst. Some examples of useful active transition metal compounds are TiCl ₂ , Ti (OCH-J) Cl-, Ti (OCH ₂ CH) CL ₃ , YCl ₃ , YOCl ₂ , VOCl ₃ and VO (OCH ₃ ) Cl ₂ . The preferred active transition metal compound is liquid under the conditions of the reaction. The preferred active transition metal compound is a titanium tetrahalide and preferably titanium tetrachloride. The preferred molar ratio of solid particulate support material to active transition metal compound is about 8: 0.4 to 8: 0.8 in the preferred embodiment of magnesium dichloride to titanium tetrachloride Better still about 8: 0.4 to 8: 0.6.

At present, it is believed that the active transition metal - preferably tetravalent titanium - in the catalyst component is not reduced to the trivalent state. Rather, it is believed that this reduction takes place in situ upon addition of the organometallic compound during polymerization.

The preferred method of the present invention contemplates the addition of the second organic donor donor compound

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This step is followed by the addition of the active metal compound (preferably titanium tetrachloride) to the resulting carrier and, preferably, a further simultaneous comminution. It is preferred to use an excess of second organic electron donor compound (preferably ethyl benzoate) relative to the active transition metal compound (preferably titanium tetrachloride). While in this regard it is believed that this incremental addition will yield a highly useful catalyst, so does the Possibility that the active transition metal compound and the second electron donor could be combined prior to adding to the catalyst support and then comminuting them together.

The so-called "permeation and mixing" of the various components of the catalyst component is preferably carried out in the absence of any solvent. The final catalyst component contains substantially the same amount of active transition metal (preferably titanium) as contacted with the solid particulate carrier during the preparation of the catalyst component. This preparation in the absence of any solvent allows the resulting catalyst component to be unreacted Extraction .. "or use laundry and thereby achieve considerable cost savings · __.

The preferred method for the preparation of the above catalyst component comprises the simultaneous comminution of the ingredients under a low-reactivity atmosphere

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a vibrating or ball mill in the absence of any solvent. Right at the beginning of the solid, particulate carrier is introduced into the mill. If the solid 'particulate' carrier contains water that needs to be removed, then a sufficient amount of a dehydrating agent is also added to the particulate carrier right from the start, at which this resulting mixture is heated at temperatures between about 0 C and about 90 C over a period of time Preferably, this mixing is done for about 6 to 24 hours (optimally over about 15 hours) at temperatures between about 35 G and about 50 ° C.

Although the common comminution can take place at temperatures between about 0 ⁰ G and about 90 ⁰ G, ~. so is but the preferred mixing temperature between '''' about 35 ⁰ C and about 50 ⁰ C. The mixing times may be between about 15 min and about .48 h vary. Preferred mixing times are about 12 ... 20 h with an optimum at about Inadequate mixing does not result in a homogeneous compound, whereas excessive mixing can cause agglomeration or a significant reduction in the particle size of the catalyst component, which in turn causes a direct reduction in the particle size of the polypropylene produced by the catalyst component.

In an alternative embodiment, a water-containing solid, particulate carrier material, the dehydrating. Agen and the second solid together in the vibrating or ball mill and comminuted together at temperatures between about 0 ⁰ G and about 90 ⁰ G Woex about 15 min to about 4Ö h away. This mixing process is preferably carried out for about 12 to 20 h (optimum at about 16 h).

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at temperatures between about 35 ⁰ C and about 50 ⁰ G.

For the preparation of the catalyst support is a first. Electron donor compound with the solid, particulate carrier, the second pesticide and optionally a dehydrating agent crushed simultaneously. Bas mixing can in.! Temperatures from about 0 ⁰ C and zvd.schen about 90 ⁰ C carried out over about 30 min to about 48 hours time. The preferred Misentemperatures are between about 35 C and about 50 ⁰ C at periods τοη about 1 ... 5 h> where one; simultaneous comminution over about 3 hours is considered optimal. · ...

- * ·.

The catalyst carrier prepared in the manner described above is added with the active transition metal compound. Although a plurality of the above-described transition metal compounds of the Pormel MO (OR) X _η is -2τ> -ΐη able to provide satisfactory catalyst components, liquid titanium tetrachloride so but as the preferred active compound is valid. Such an active transition metal compound is added to the vibratory mill or ball mill and comminuted therein together with the catalyst carrier. This mixing can be "at temperatures of about 90 ⁰ C .... Θ carried out over about 15 minutes to about 48 hours time. .It is preferred that this mixing at temperatures between about 40 ... 80 ⁰ C for about 12. ... takes place for 20 h (optimum at about 16 h) in order to recover the very active supported catalyst component.

In an alternative embodiment of the invention, a second electron donor compound corresponding to or different from the first electron donor compound can be prepared prior to the reaction of the transition metal:

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Bond are comminuted together with the catalyst support. In the preferred embodiment ethyl benzoate is co-in. The ball or vibration mill with the catalyst support at temperatures of about 0 ... 90 ⁰ G over a period of. crushed for about 15 minutes to about 48 hours before adding the titanium tetrachloride. Preferably, however, the mixing is carried out at about 35 ... 50 ⁰ G over a period of about 1 · .. »5 h. but especially about 3 hours.

In a further alternative embodiment of the invention, the second electron donor compound, so z. As ethyl benzoate, premixed with the active transition metal compound, so as titanium tetrachloride, are ,, before these components are added to the catalyst support "this: premix is then added to the * catalyst support under those conditions and those mixed periods of time as above · ., specified for the active transition metal compound.

The solid titanium-containing catalyst component of the present invention, preferably obtained after simultaneous comminution of the above-mentioned ingredients, has outstanding properties over previously known catalyst components. Ei® such catalyst component is a highly effective supported catalyst component for the polymerization of alpha-olefins. The catalyst component of the present invention has a very low specific surface area of less than 1 m / g. Although the catalyst component of the present invention is handled in an anhydrous, low-reactivity atmosphere, according to the comparative products of the prior art

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It should also be a fact that the-. The catalyst component is less reactive and produces less harmful decomposition products than those comparative catalyst components, thus representing a product of greater application security.

The solid catalyst component powder prepared by the method described above can be subjected to long-term storage with little or no loss of activity

become. , -

It. it is believed that the active transition metal (preferably tetravalent titanium) in the catalyst component does not reduce to the trivalent state. More, it is believed that this reduction takes place in situ after the decomposition of the organometallic compound during the polymerization.

The catalyst component produced by the above methods is used in conjunction with a cocatalyst, an organometallic compound, and optionally another organic electron donor compound to produce sterically uniform polyolefins. The organometallic cocatalyst is selected from the group consisting of the aluminum alkyls, the alkylaluminum halides, and the alkylaluminum hydrides. The preferred cocatalysts are the aluminum trialkyls, in particular triethylaluminum and triisobutylaluminum, in which case triethylaluminum is again particularly preferred. The preferred molar ratio of organometallic cocatalyst to the titanium-containing catalyst component, ie preferably the ratio

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from Mol Triethy Aluminum to Grams Titanium in the catalyst component of the present invention is about 50-300: 1, more preferably about 240: 1. The organic electron donor compound is selected from the same group which also includes the electron donor. ., Compounds of the titanium-containing catalyst component were selected, these two donor compounds may be the same or different.

Preferred electron donating compounds are selected from the alkyl esters of carboxylic acids such as ethyl anisate, methyl p-toluate or ethyl benzoate. The most preferred electron donor compound is methyl p-toluate. The preferred molar ratio of electron donor compound to titanium-containing catalyst component, preferably moles of methyl p-toluate to gram atoms of titanium, is about 60 for the catalyst component of this invention. ..120: T, better about 70 ... 96: 1. -

A catalyst prepared by the foregoing term can be used in the standard process of polymerization of alpha olefins. The catalyst can be used where the preparations are in the liquid tank, in an inert solvent or in a gas phase. Essentially, the standard operating conditions can be used in these various polymerization processes. In this case, the catalyst of the present invention produces polypropylene having an isotactic index of at least 80, better still 90, most preferably 93 or more, a total ash content of

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not more than about 700 ppm, more preferably not more than about 300 ppm, and having a magnesium residue of less than about 20 ppm.

The preferred mode of use for the catalyst of the present invention is polymerization in liquid basins. In this mode of use, the complicated steps of polymer-based polymerization, polymer ash removal and the associated solvent recovery are eliminated in polypropylene production

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Most recent catalyst orconceptors have required an extraction step in the process of their preparation

made. The catalyst component of the present invention, which can be prepared in the absence of a solvent, eliminates such a step ... and thereby not only significantly reduces the capital expenditures for the plants for their production, but also reduces the running costs of operation Not only are the important economic benefits mentioned above achieved with all this, even 'significant energy savings and reductions in environmental impact are achieved.

Another characteristic feature of the catalyst component carrier of the present invention refers to other economic advantages. By using a dehydrating substance vri.rd namely the use of more expensive and more difficult to handle anhydrous magnesium chloride repealed.

The catalyst component of the present invention may also be used in conjunction with various specifications relating to a polymer

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with less fine particle content, d. H. Sieve number 200 or below to be obtained · This is important in view of reducing the polypropylene waste due to fine powder loss as well as the reduction of. Handling problems associated with fine powders. Varying the milling times in the preparation of the catalyst component of the present invention makes it possible to achieve the desired coarseness of the particles of the catalyst and thus also of the polymer produced.

The catalyst of the present invention provides high productivity in terms of yields between about 3600 and about 8,100 kg (8,000 and about 18,000 lb.) of polymer per pound. Catalyst or from about 18,000 to 408,000 kg "(400,000 ... 90000 Ib.) Polymer per Ib. Titanium. This ge. Increased productivity also reduces catalyst consumption. It also reduces the catalyst residue in the final polypropylene product and thus eliminates the need for polymer deashing. The high isotacticity of the produced polymer also precludes the elimination of the expensive step of polymer extraction and solvent recovery required in liquid polymer monomer polymer manufacturing processes. , -. ,

The catalyst of the present invention produces a highly heterogeneous polypropylene polymer having an isotactic indium of generally greater than 90, preferably 93 and greater, with a low catalyst residue, having a total ash content of less than about 700 ppm, and one magnesium content

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less than about 20 ppm. In addition, the polymer size distribution being such that fit through the a-,] _S ^eme i ^NEN less than about 5% of the polypropylene produced through a sieve of mesh width 140th These properties of the polymer produced permit industrial use without the elaborate steps of polymer extraction and polymer deashing, which in turn finds considerable cost savings.

Frequently, hydrogen is used to control the molecular weight of polymers. In the process of polyprppylene production, the present catalyst component produces a polymer having a desirable molecular weight distribution at lower hydrogen pressures than is generally the case in other manufacturing processes.

embodiments

The following embodiments, by way of illustration of particular embodiments of the present invention, are intended to illustrate the invention and not to limit it in any sense. The polymer size distribution for the polypropylene prepared with the following catalysts are shown in Table I. ,

Exemplary embodiment 1

Anhydrous RügClp was prepared by drying at 350 ⁰ C for 4 h period while an HCl blanket. ' This anhydrous igClg was mixed in an amount of 25 g with 4.34 g of AlCl 2, and 7.01 g of anisole under nitrogen.

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atmosphere of a vibrating ball mill of 0.6 l capacity and with 316 pieces of stainless steel balls totaling 3250 g are entered in a ball diameter of 12 mm. This mixture was comminuted for 24 hours without temperature control. Niumtetrachlorid had been pre-mixed at about 50 ⁰ C Tita-? With ethyl benzoate (SB) in n-heptane. 6.19 g of this TiCl,. EB complex was then added after 24 hours of co-crushing of the aforementioned substances of the vibrating ball mill, the mixture thus obtained was then comminuted for a further 20 h at ambient temperature and under a protective gas atmosphere. In this way, a solid catalyst component was formed which could be used without extraction or catalyst washing.

A sample of the catalyst thus prepared was tested in the solid propylene polymerization test. To this were added, 22.9 mg

X ' ν

of the triethylaluminum (TEAL) cocatalyst, 120 mg ^{. of} methyl p-toluate (MPT) and 20 mg of the catalyst component were added to a 1 liter stainless steel autoclave provided with a stirrer. Otherwise, dilute solutions of TEAL and MPT can operate at temperatures below about 25 ⁰ C for about 5 min * ..10 be long pre-mixed prior to addition of the catalyst * The TEAL / Ti ratio was 240/1, and the TEAL / MPT ratio was 2.5. The reactor was then charged with 300 g of liquid propylene. The polymerization took place at about 70 ^° C. for one hour. At the end of this period, a little unreacted propylene was quenched and the resulting polypropylene was withdrawn. 156 g of polypropylene were produced, which corresponded to a yield of 7800 g of polypropylene per gram of catalyst or 390000 g of polypropylene per gram of titanium.

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- 25 -

For the purpose of determining the isotactic index, a fraction of the boiling n-heptane polymer was extracted for 16 hours in a Soxhlet extractor, and the insoluble fraction was dried. The isotactic index of this polymer was 86.0.

Embodiment 2 . ·

A catalyst prepared according to the procedure of Example 1 was tested with the liquid propylene polymerization test also described in Example 1, wherein the amount of the p-type pluate used was varied. In this test, only 100 mg of IPT was used, giving a TEAL / MPT ratio of 3.0. The productivity reached 10250 g of polypropylene per gram of titanium. The isotactic index, however, was only 69.0. ,

Embodiment 3

A catalyst prepared by the procedure of Example 1 was tested by the liquid polymerization test also described in Example 1, substituting 90 % ethylanisate for the methyl p-toluate in the liquid propylene polymerization . The TEAL / EA ratio was 4.0. The productivity of the catalyst under dry conditions reached only 3750 grams of polypropylene per gram of catalyst or 18750 grams of polypropylene per gram of titanium with an isotactic index of 89.0. -

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Embodiment 4

A catalyst was prepared and tested according to the procedure outlined in Example 1, but using 5 ₉ 32 g of anisole and 4.59 g of TiCl 3. BB complex. The catalyst showed a productivity of 5250 g of polypropylene per gram of catalyst (262500 g of polypropylene per gram of titanium) and an isotactic index of 81.3 x

Embodiment 5

In accordance with the procedures set forth in Example 1, a catalyst was prepared and tested but containing 20.0 g of AlCl, 3.50 g of AlGl, 2.84 g of Anisql

and 4.36 g of TiCl.-EB complex were used. The catalyst disclosed a productivity of 4400 g of polypropylene per gram of catalyst (220,000 g of polypropylene per gram of titanium) and an isotactic index of 83 »2.

TABLE I ». Polymer size distribution

(Percent of polymer on mesh screen)

Exemplary mesh size

Game 20 40 80 140 200 325 Pan

5. ·

- 27

54 25 17 3 0 0 0 45 32 20 3 0 0 0 51 20 14 7 VJL 3 1 51 27 17 4 1 0 0 40 27 24 7 2 0 0 32 29 26 9 3 1 1 43 29 22 VJL 1 0 0 45 33 19 ' 3 1 0 0

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-ar-

Ausf iitiruigs - 20 40 80 140 200 325 pf example 23 25 28 13 7 4 1 16 40 26 23 8th 2 1 0 17 , 38 26 22 9 3: 1 1 19 41 25 • 23. 1 3 1 0 20 31 26 26 12 4 1 0 .21 .37 27 25th 8th 2 1 0 22 37 28 25 7 2 ,1 0 23 43 25 21 8th 2 1 1 '24 .38 30 24 5 2 1 1 25 I 42 26 19 7 4 2 1 26 - ... 50 27 18 .5 2 1 0 2'S 51 24 14 5 3 2 1 2 B 63 20 13 3 1 0 0 31 78 15 6 1 0 0 1 32 44 18 21 -9 5 * 3 2 38 (7 h) 59 22 15 3 1 1 0 38 (10 hours) In the same year 6

According to the procedures set forth in Embodiment 1, a catalyst was prepared and tested but containing 30 g of HgCl ₂ , 3.00 g of AlCl 4, 4.87 g of anisole, and 6.26 g of TiCl ₂ . The EB-Komples were used. The catalyst showed a productivity of 3900 g of polypropylene per gram of catalyst (195000 g of polypropylene per gram of titanium) and an isotactic index of 90.2 ×.

Embodiment 7 , '.

According to the procedures set forth in Embodiment 1, a catalyst was prepared and

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However, 20.0 g MgCl, 1.17 g AlCl, 2.84 g anisole and 4.05 g TiCl..EB complex were used. The catalyst showed a productivity of 2800 g of polypropylene per gram of catalyst (140,000 g of polypropylene per gram of titanium) and an isotactic index of 85.6.

Embodiment 8

In a similar manner to the embodiment 1 Vorgeh ens, a catalyst was prepared and tested according to the manner described in Example 2. 30 g of MgCl ₀ , 5.25 g of AlCl 3, and 3.53 g of anisole were comminuted together for 10 h. Subsequently, the addition of 6.41 g of TiCl ₂ , EB complex and further comminution were carried out over 20 h. The yield was 3900 g of polypropylene per gram of catalyst (195000 g of polypropylene per gram of titanium) with an isotactic index of 92.4 x

χ \

Embodiment 9

According to Embodiment 8, a catalyst was prepared and tested except that the anhydrous MgCIp was not HCl-dried and the initial milling time was 15 hours. The yield reached 4,800 g of polypropylene per gram of catalyst (240,000 g of polypropylene per gram of titanium) at an isotactic index of 91.9 x

Embodiment 10

According to Embodiment 9, a catalyst was prepared and tested except that 3.50 g of AlCl, 8.37 g of anisole and 7.00 g of TiCl.'EB complex were used. The yield was only 1100 g of polypropylene per gram

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Catalyst (55000 g of polypropylene per gram of titanium) at an isotactic index of 92.0. ,

Embodiment 11

According to an embodiment .9 .The catalyst was prepared and tested., But -wobei_ the mill gate adding the TiCl, "EB-complex at about 90 ⁰ C was heated. The yield was 4250 g of polypropylene per gram of catalyst (212500 g of polypropylene per gram of titanium) with an isotactic indices of 88.5 * "-.

Example 12 '"-V-.'.

According to Example 9 ", a catalyst was prepared and tested, however, the final milling time was also 15 hours The yield was 4900 g of polypropylene per gram of catalyst (245000 g of polypropylene per gram of titanium), with an isotactic index of 92.8. .: .-

Embodiment 13 ; , ....

According to Embodiment 12, a catalyst was prepared and tested using, however, 7.05 g of anisole and 7.00 g of TiCl * EB complex. The yield was 4000 g of polypropylene per gram of catalyst (200000 g of polypropylene per gram of titanium) at one isotactic index of 93.4. .. - ^; : '·. , ; , - -

Out of the game 14 ... -. , , ^:

Similar to that in Ausführungsbeispiä. 9 described procedure. '. '.-' - ^: '·:,' -: - 30 -

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Example, a catalyst was prepared and tested, with the final Vermüsungsζeitspanne was 10 hours. 28.7 g of anhydrous HgCl were used _? , 6.52 g. AlCl- ,, 5.28 g anisole and 6.70 g TiCl. "EB complex. The yield was 3450 g of polypropylene per gram of catalyst (172500 g of polypropylene per gram of titanium) with an isotactic index of 94.0."

Embodiment 15

According to Example 14, a catalyst was prepared and tested, although 22.0 MgCl ₂ , 7.89 g. AlCl ₃ . 3.53 g of anisole and 5.55 g of TiCl ₄ .multidot.O.sub.2 ex were used and the mill was heated to about 90.degree. C. before adding the TiCl.sup.1B complex. The yield achieved

2000 g of polypropylene per gram of catalyst (100000 g of polypropylene per gram of titanium) with an isotactic. Index of 87.7. , (*

Exemplary embodiment 16

Anisole and AlCl ,. were precomplexed; 6.34 g of this complex were comminuted for 24 hours in the mill according to Example 1 together with 20 g of anhydrous MgCl ₂ . Subsequently, a quantity of 4.36 g TiCl, -ΞΒ-complex was added to the mill and comminuted for a further 20 h. The resulting catalyst was tested according to Embodiment 1 and showed a yield of 2319 g of polypropylene per gram of catalyst (115950 g of polypropylene per gram of titanium) at an isotactic index of 92.6. -.--

Embodiment 17

30.0 g of anhydrous MgCl ₂ , 5.25 g of AlCl ₃ and 3.53 g of anisole

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were comminuted together according to Embodiment 1 over 15 h. Then 3 »19 g of ethyl benzoate was added to the mill and the resulting mixture was comminuted for a further 10 h. Finally, 4.00 g of TiCl were added. and a final grinding over 15 h away. The catalyst tested according to Embodiment 2 gave a yield of 3800 g of polypropylene per gram of catalyst (190000 g of polypropylene per gram of titanium) at an isotactic index of 92.7 *

Embodiment 18 _ί

According to Embodiment 17, a catalyst was prepared and tested, except that the final Yermahlungszeit was only 10 hours. The yield reached 2050 g of polypropylene per gram of catalyst (102500 g of polypropylene per gram of titanium) with an isotactic index of 92.7.

Embodiment 19

According to Embodiment 17, a catalyst was prepared and tested, except that 5.17 g of ethyl benzoate was added to the improved carrier and comminuted with it for only 5 hours. This was followed by the addition of 3.78 g of TiCl3 and further co-milling for 15 hours. The yield was 5500 g of polypropylene per gram of catalyst (275,000 g of polypropylene per gram of titanium) at an isotactic index of 92.4.

Embodiment 20 .

According to Embodiment 19, a catalyst was used

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- 32 -

made and. tested, but, after adding the TiGl, the mill was heated to about 90 ⁰ G. The yield was reduced to 3500 g of polypropylene per gram of catalyst (175,000 g of polypropylene per gram of titanium) at an isotactic index of 92.7.

Embodiment 21

According to Embodiment 19, a catalyst was prepared and. tested, however, the grinding time after. Add, the Ethylbenzoats only 4 h and the ITermahlungszeit after adding the TiCl. on 16 h. The yield was only 3700 g of polypropylene per gram of catalyst (185000 g of polypropylene per gram of titanium) with an isotactic index τοπ ^ 93.2 ·· · Ϊ. ,

Embodiment 22 * ^v X

According to Embodiment 21, a catalyst was prepared and tested, except that 5.89 g of ethyl benzoate and 3.83 g of TiGl. were used. The yield was 3750 g of polypropylene per gram of catalyst (187500 g of polypropylene per gram of titanium:) at. an isotactic index of 94.5 ·

Embodiment 23

A catalyst was prepared and tested according to Example 19, except that the milling time was only 2 hours after adding the ethyl benzoate and the mill was heated to about 90 ^° C. before adding the ethyl benzoate. The yield was 3400 g of polypropylene per gram of catalyst (170000 g of polypropylene

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230952 8 -33-

per gram of titanium) at an isotactic index of 94.3 x Example 24

According to Example 17, a catalyst was prepared and tested, except that 4.58 g of anisole, 5.89 g of ethyl benzoate and 3.94 g of iCl. was used. Bach adding ethyl benzoate was ground for only 2 hours; after adding the TiCl 2. was married for 16 hours. The yield reached 4100 g of polypropylene per gram of catalyst (205,000 grams polypropylene per gram of titanium) _with> one isοtaktischen Indes of 93 "7 ·

Embodiment 25

30.0 g of anhydrous UgCl ₂ and 5.25 g of AlCl were comminuted together over 16 hours as in Example 1. After subsequent addition of 5.89 g of ethyl benzoate, the resulting mixture was ground for a further 4 hours. Finally, a quantity of 3.50 g TiCl, was added and additionally ground for 15 h. The catalyst tested according to Example 2 gave a yield of only 1750 g of polypropylene per gram of catalyst (87500 g of polypropylene per gram of titanium.) With an isotactic index of 88.4 ×

Embodiment 26

According to working example i, 30.0 g of anhydrous MgCl ₂ Cl ₂ and 3.00 g of anisole were comminuted for 4 hours. "Sun was followed by the addition of 5.18 g of ethyl benzoate followed by Yennahlen over 15 hours. Finally, a addition of 3.30 g of TiCl was carried out with additional monomers

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over 15 times. The catalyst tested according to Embodiment 2 showed a yield of 4100 g of polypropylene per gram. Catalyst (205,000 g of polypropylene per gram of titanium) at an isotactic index of 91.2.

Embodiment 27

According to working example 1, 30.0 g of anhydrous MgGIp were comminuted directly together with 5.18 g of ethylbenzoate for 15 h. The addition of 3.times.10 g of TiGl and additional milling of the resulting mixture over 15 hours were then carried out. The catalyst, when tested according to Embodiment 2, yielded only 3000 g of polypropylene per gram of catalyst (150000 g of polypropylene per gram of titanium) at an isotactic index of. 90.6. '

iX embodiment 28 . " ^J '·"

In. of the mill of embodiment 1, 30.0 g of anhydrous ISUgGl ₂ with a H ₂ 0 content of 6.63 % under a nitrogen atmosphere together with 7.01 g SiGl. Crushed for 16 hours. Then, adding 5.25 g of AlCl and 3.53 g of anisole and 15-hour Y milling, adding 5.17 g of ethyl benzoate and 5 hours of grinding, and finally adding 4.45 g of TiCl, and further grinding for 15 hours. The catalyst tested according to embodiment 2 gave a yield of only 36 g of polypropylene per gram of catalyst (180,000 g of polypropylene per gram of titanium) at an isotactic index of 91.1.

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Embodiment 29

According to Embodiment 28, a catalyst was prepared and tested, however, the initial Yermahlungsseitspanne was only 15 h and also the grinding after addition of the Ethybenzoats was limited to only 3 h. The yield was reduced to 1850 g of polypropylene per gram of catalyst (92500 g of polypropylene per gram of titanium) at an isotactic index of 90.5 ×

Augmentation Example 30

According to Embodiment 28, a catalyst was prepared and tested, except that 14.03 g of SiCl. The turnaround times were 18 h, 17 h, 2 h and 15 h. A yield of only 2250 g of polypropylene per gram of catalyst (112500 g of polypropylene per gram of litanium) was achieved at an isotactic index of 90.8.

Embodiment 31 ...

According to Embodiment 28, a catalyst was prepared and tested, except that the EUO content of MgCl _{2 was} only 0.35%, only 1.00 g of SiCl ₄ or 3.87 g of ClCl. The yield reached 5900 g of polypropylene per gram of catalyst (295000 g of polypropylene per gram of titanium) at an isotactic index of 94.5 *. The yield was 4 h, 15 h, 3 h and 15 h Plüssigkeitsbecken polymerisation tests under different hydrogen pressures for the determination of the effect ύοώ. Hydrogen pressure or productivity, isotactic index and

- - 36 -

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Melt flow performed. The results of these tests are shown in Table II.

TABLE II Effect of Hydrogen pressure during the pole Isotact, index (*) Melting flux (dg / M) polymerization 94.5 0.4 Hydrogen (psig) Plüssigk.- basin productivity (g PP / g Eat ·) 93.4 0.7 Exemplary embodiment 31 0 6000 92.7 1.8 5 7500 92.4 4.2 10 7250 92.3 4, p 15 7200 91.0 10, ΐ 20 5500 90.5 25 5900 95.6 0.18 35 6200 93.9 1.25 .. Example embodiment 32 0 8000 93.3 3.68 5 8900 92.2 3.81 10 7900 92.0 14.58 , '- ¹⁵ 8300 89.0 30.92 25 8650 35 9800 Embodiment 32

Anhydrous MgGl ₂ was prepared by drying at 350 ° C for 4 hours (made under an HCl blanket - 2500 g of this anhydrous MgCl ₂ - was fed with 438 g of AlGl 2 under a blanket nitrogen gas atmosphere of a Vibratom mill

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- 37 -

had a capacity of 10.0 1 and 2250 stainless steel balls of 144 kg total mass and a ball diameter of 2.54 cm contained. This mixture was comminuted for 16 h at 35 ^° C. This was followed by addition of 294 g of anisole and further .Vermählen at 35 ⁰ G rate over 3 hours; Thereafter, 493 g of ethyl benzoate were added, whereupon at 35 ⁰ C for a further 3 ii long was ground; Finally, a addition of 320 g of IiGl. and an hourly grinding at 62 ⁰ CvO: - ...

The catalyst tested according to working example 2 yielded 8000 g of polypropylene per gram of catalyst (400,000 g of polypropylene per gram of bitanium) at an isotactic indices of 95.6. Additional tests under a hydrogen atmosphere to determine the effect of the drum were first off pressure on the Produktisrität, the iso tactical Meanwhile and the S _c hmelzfluß are shown in their .Ergebnissen in Table II. The polymer residues on some inorganic substances are listed in labelle III.

EABEELE III polymer residue from embodiment 32

ELüssigkeits total

basin-product- ash

tivity (ppm) (g PP / g Bat.)

8900 590

8300 642

, 8650 465

9800 630

The catalyst components prepared in accordance with Example 32 are analyzed with respect to their specific surface area using the In.3? .- method. R .... ':' ^: - \ ν Ζ; "-" - 38 -

mg Ti al (Ppm) (Ppm) (Ppm) 18 3 220 15 2 310 15 3 245 15 3 325

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- 38 -

· The specific surface area proved to be low,

less than 1 m / g. Representative specific surface areas of catalyst components prepared according to Example 32 were 0.64, 0.80 and 0.94 m ² / g.

These areas were determined using nitrogen. Other catalyst components prepared in the same way were examined for their specific surface area both with the aid of nitrogen and with the aid of krypton. The surface values determined under nitrogen use were 0.55, 0.85, 0.62 and 0.79 m / g; the corresponding values obtained with the aid of krypton were 0.25, 0.40, 0.28 and 0.26 m ² / g.

In another example, were the specific surfaces during different steps of manufacturing? a catalyst component according to embodiment. The specific surface was, after the milling of magnesium dichloride and aluminum trichloride, 4 * ·· 6 m / g. After the addition and grinding of anisole, the specific surface area was reduced

1.25 and 1.65 m / g · After further comminution with ethylbenzoate was:! the specific surface still

decreased more and amounted to 0.62 and 0.72 m / g.

Finally, after grinding with titanium tetrachloride

the specific surface area was 0.76 m / g.

Embodiment 33

A sample amount of the solid catalyst component prepared according to Embodiment 32 was used in heptane high pressure

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Polymerization tested. To this end, a stainless steel autoclave (1.0 liter capacity) equipped with stirrer was charged with 500 ml of heptane. Uun 290 mg of triethylaluminum (TEAL) were introduced, wherein 3 minutes at 20 ⁰ C was stirred. This was followed by the addition of 120 mg of methyl p-toluate (MPT). under 3minütigem also stirring at .20 ⁰ C. Then 20 mg of the corresponding embodiment were added 32 prepared catalyst component. Bun added 81 ml of hydrogen in the physical state and propylene (10 at - 150 psig) with increasing temperature to 70 ° C. The polymerization was carried out at 70 ° C for about 2 hours. At the end of this period, the unreacted propylene was withdrawn and the polypropylene produced was processed by filtration. , , The amount of soluble in the polymerization solvent. Polymer was determined by evaporation of an aliquot of solvent. The catalyst produced 7155 g of polypropylene per gram of catalyst (35775Og of polypropylene per gram of titanium) at an isotactic mean of 93.8 and a heptane soluble content of 2.7 %.

In a second test, 162 ml of hydrogen were used in the physical hormone state. The catalyst produced 6075 g of polypropylene per gram of catalyst (303750 g of polypropylene per gram of titanium) with an isotactic index of 90.0 and a heptane-insoluble content of 4.4%. , , ,

Embodiment 34 _:

According to Example 32, a catalyst was prepared, although commercially anhydrous

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Magnesium dichloride was used. The amounts of AlCl- ,, anisole and ethyl benzoate were also varied · 2500 g of commercial wasserfreies.igCl "and 656 g AlCl ^ 16 were crushed together hours at 30 ⁰ G. To this mixture was added 44-3 g of anisole; then, a three-hour grinding was carried out at 30 ⁰ C. Then, the final addition of 319 g TiGl. and a 16 hours' grinding of the mixture at 60 ° C.

The catalyst was tested according to Example 32, except that 88 mg MPT was used and the hydrogen pressure was 0.7 at (10 psig). The catalyst yielded a high yield of 11,300 grams of polypropylene per gram of catalyst (642,000 grams of polypropylene per gram of titanium) with an isotactic index of 92.7. As polymer residues, 13 ppm magnesium, 2 ppm titanium, 22T ⁴ PPm aluminum, and 586 ppm Total ash determined ·

Embodiment 35

According to the procedure in Embodiment 32 , a catalyst was prepared and tested. 2500 g MgKL "with 1.17 % water content, 275 g SiGl _A and 656 g AlGl-,

ο were entered into the mill and milled at 40 G for 16 h. Then, by the addition of 393 g of anisole and other three-hour milling at 45 ⁰ G * Do by the addition of 494 g of ethyl benzoate and more three-hour milling at 48 ⁰ G. Finally took place the addition of 321: g TiCl. with heavier milling for 58 hours at 58 ° C. When tested under H ₂ at 1 atm (15 psig), this catalyst produced 8,000 grams of polypropylene per gram of catalyst (400,000 grams of polypropylene per gram of titanium) with an isotactic index of 89.9 · ·

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Embodiment 36 .

The vibratome mill of Example 32 was dried under a nitrogen atmosphere with 2660 g MgCl ₂ (4.98 % water content) and 1036 g SiCl. fed. This mixture was milled 21.5 hours together at 35 ⁰ C * Then, 466 g of AlCl, added to, the crushing was continued at 35 ° C 1.0. l? un clogging occurred clay 313 g anisole and further milling at 35 ^G C over 19.5 h. time. Thereafter, 525 g of ethyl benzoate were zugesejtzt, whereupon a further 5.0 h at 35 C was milled »Finally, the addition of 341 g of TiCl. with final grinding at. 35 ⁰ C over 19.0 h "Sun was sampled; the remaining amount was ground for a further 6.0 h.

The catalyst of the first sampling, when tested according to Embodiment 2, yielded 3650 g of polypropylene per gram of catalyst (182500 g of polypropylene per gram of titanium) with an isotactic index of 93.4. The second sampling catalyst returned only 2550 grams of polypropylene per gram of catalyst (127500 grams of polypropylene per gram of titanium) with an isotactic index of 94.2.

Exemplary Embodiment 37

According to the procedure of embodiment, a catalyst was prepared and tested, however, the magnesium chloride contained only 1.17 % water = and only 185 g SiCl. were used. Instead of the quantities mentioned in Example 35, 369 g AlClU, 249 g anisole, 416 g ethyl benzoate and 271 g TiCl. used ,.

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5 2

- 4-a, -

The polymerization results corresponded to those of the embodiment 36 *

Embodiment 38

The Yibratom mill of Example 32 under a nitrogen blanket gas atmosphere was 5000 g MgGl ₀ (1.17 % water content) and 552 g SiCl. entered. This mixture was comminuted for 16.0 hrs. On 28 x 55 g. Next, 875 g of AlCl and 1 hr of Y-milling were added at 28 x 55 ° C, 588 g anisole added, and 3 hr Yermahlen at 53 ·· -63 ⁰ C, addition of 986 g of ethylbenzoate and 3sterm Yermahlen at 53 ··. 63 ° C, adding 640 g of TiCl. and Yermahlen at 63 ° C for periods of 7.0; 3.0; 4.0 and finally again for 3.0 h, samples of the catalyst component being taken for test purposes after each of these periods. The catalyst was sampled in accordance with Example 2, but maintaining a hydrogen pressure of 1.7 at (25 psig) in the autoclave Productivity and isotactic index are shown in Table IY.

TABLE IY Liquid Pool Polymerization

TiCl. Productivity iso-

Yermahlunffszeit Ch) <S ^ρρ / δ'ΐ g (.P, P / gtakt ·

Run 7.0 (25 psig H ₂ ) 4800 240000 90.0

Example 38 10.0 »5850 292500 91.1

14.0 5800 290000 90.2

17.0 « 5750 287500 91.0

17.0 (no H ₂ ) 4750 237500 95.6

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230952 8 -43-

Forts. Tab. IV -

TIGL. Productivity iso-

Milling time (h) (g PP / g (g PP / g -JfS **

Cat.) Ti) ^and ·

Implementation example 7,0 (no game 39 10,0 "

13.0. "18.0? 23.0"

Embodiment 39 - - -.

According to Embodiment 35, an e-catalyst was prepared and tested, but using only 2500 g BSgCIg. In variation of the procedure were

2500 125000 96.3 3600 180000 95.6 4250 212500 94.1 4750 23750 © 93.8 3500 175000 94.5

and SiCl. 5.0 wed h at 35 * »» 7O ⁰ C; after addition of AlCl- was ground for 1 h at 35 ° G, after addition of anisole was ground at 35 x * · 7Ο ° G for 3.0 h, after addition of ethylbenzoate was also 3.0 h at 35 × * »70 ⁰ C milled. The grinding temperature after the addition of TiCl. was 35 · ..70 ⁰ C, here sample amounts of the catalyst component were taken after 7.0 h, 10.0 h, 13.0 h, 18.0 h and 23 »0 h. ^;

The results of the polymerization test are shown in Table TV . ''. ,

Embodiment 40

The vibrato mill of Embodiment 32 was charged with 2500 g MgGl ₂ (0.16 % water content) and 37 g SiGl. under a nitrogen blanket gas atmosphere. This mixture was ground at 52 ^° C. for 5.0 hours. Followed by: addition of 438 g AlGl, and 1 hour at 60 ⁰ G, addition

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23 0 9 52 8.

of 294 g AnisoL and 3 hours of grinding at 70 C, addition of 494 g of ethyl benzoate and 3 hours of milling at 75 ⁰ G and finally addition of 323 g of TiCl. and 18 hours at 92 ⁰ C, then first sampling and then additional 1-hour grinding at 32 ⁰ C.

The catalyst was tested according to Example 38. The productivity of the first sampling amount was 4600 g of polypropylene per gram of catalyst, 230000 g of poly propylene per gram of titanium at a jsotactic index of 87.2o The second sampling achieved a productivity of 5100 g of polypropylene per gram of catalyst (255 g of polypropylene per gram of catalyst) Gram of titanium) with an isotactic indes of 93 »9.

Embodiment 41 . 't

A sample amount of a catalyst component prepared according to Example 32 was tested in-tion.von% ethylene of the polymer .. A jacketed and equipped with magnetic stirrer 1-1 autoclave was stirred at 25 ⁰ C.mit; flushed ethylene. 194 mg of triethylaluminum (TEAL) and, subsequently, 16 mg of the catalyst component prepared according to Example 32 were fed to this autoclave. The catalyst component wurde.in form of a 40 mg / ml dispersion in mineral oil added The autoclave was pressurized with hydrogen to a pressure of 4.5 atmospheres (65 psig) · Well-were ^the: autoclave sowie'darauffolgend under-pressure 500 ml of isobutane Fed ethylene; The reactor contents were brought to a total pressure of 35 at (500 psig) Fe 8-5 ⁰ G. After one hour the polymerization was terminated, the isobutane and unreacted ethylene

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was withdrawn, the produced polyethylene was shown.

The catalyst produced 9700 g of polyethylene per gram of catalyst (4-85000 g of polyethylene per gram of titanium). The melt index of the polymer was 3.1 g per 1 min, the density reached 0.9694 g per cm, the Mw / Mn ratio was 6.2.

Embodiment 4-2

The polymerization according to embodiment -4-1 was repeated, but the polymerization was carried out over 4 hours. Beer Catalyst produced 20800 grams of polyethylene per gram of catalyst (104-0000 grams of polypropylene per gram of titanium) during this period. The catalyst productivity was thus 5200 grams of polyethylene per gram of catalyst per hour (260000 grams of polyethylene, per gram of titanium per hour). The melt index of the polymer reached 8.8 g per 10 min, the density was 0.9666 g per cnr. the Mw / Mn ratio was 4-9.

Execution at game 4-3

The polymerization of Example 4-1 was repeated, but instead of triethylaluminum triisobutylaluminum (TIBAL) used as a cocatalyst. has been. Furthermore, 20 mg of the catalyst component prepared according to Example 32 were used, the hydrogen pressure being raised to 3.5. at (50 psig). The catalyst produced 7300 g of polyethylene per gram

12 »_12. 1981

C 08 P / 230 952/8

ο - »η η ε ο ο ^{59 225 18}

23 0 9 52 8 _

Catalyst (365000 g of polyethylene per gram of titanium) "The melt index of the polymer was 0.9 g per 10 min, the apparent O reached .9593 g per cm-% Mw / Mn ratio was 5» 0 *

Execution sbeis-piel 44

According to the procedure of embodiment 1 was; prepared a catalyst and tested in bulk polymerization of 1-butene. Into a stirred 1-1 autoclave, 229 mg PART, 100 mg ...., MPT and -20 mg of the catalyst were introduced. The autoclave was pressurized to 0.7 atm (10 psig) and then charged with 500 ml of 1-butene. The polymerization was flared at 40 ⁰ O exceeds 2 hour period durchgeführt- ^ Thereafter .wurde not gone in the reaction of 1-butene ", the resulting polybutene was prepared. The catalyst produced 64 g polybutene at a yield of 3200 g polybutene per gram of catalyst. At I6stündiger extraction by boiling diethyl ether in one. Soxhlet extraction apparatus showed "that the ether-insoluble fraction of the polymer produced constituted 94-4 % ".

In view of the above description and embodiments, further modifications and alternative embodiments of the present invention should become apparent to those skilled in the art. For example, it may prove advantageous to use the liquid reactants. such as methyl phenyl ether, ethyl benzoate and titanium tetrachloride, during the initial 60 minutes of each stage of milling by metered spraying, slowly adding so as to form

230952

12. 12. 1981 C 08 F / 230 952/8 _ü> 59 225 18

to avoid a paste-like mixture of the ingredients. Moreover, the foregoing descriptions and exemplary embodiments are presented for purposes of illustration and illustration only; they are intended to teach and enable those skilled in the art to utilize the present invention.

While the preferred embodiment is considered to be the best mode of realization at present, it is by no means the only "possible embodiment. It will be apparent to those skilled in the art that a variety of modifications and variations of this specific method and composition have been made If, for example, the catalyst applied for 1 can also be used for Po isomerization, it is possible to deviate from the scope and spirit of the present invention

other olefins than only the alpha olefins be suitable.

In addition, carriers other than magnesium chloride may have other active transition metal compounds than straight titanium tetrachloride economic utility. It is the applicant's intention to include such modifications and variations as fall within the spirit and scope of the present invention with the following claims.

Claims (14)

230952 B Berlin, 12.1.1983 59 225/18 Erf indungsans pru.cn A process for preparing a catalyst support useful for use in alphaolefin polymerization, characterized in that A) a first titanium-free, particulate substance suitable for use in the alpha-olefin polymerization is passed through with a second solid to form a titanium-free, particulate carrier mixture, whereby this second pesticide differs from said first particulate substance, but substantially the same structural Structure and, after this penetration, the thus obtained particulate carrier mixture has an organic electron donor compound. j
wherein at least a portion of said slektronendonator compound reacts with said second solid at least on the surface of said particulate carrier mixture to thereby produce a titanium-free solid particulate catalyst carrier having a lower specific surface area than said particulate carrier mixture on v / eist, or B) (a) a titanium-free, solid, particulate catalyst support is produced, which is composed of (i) a magnesium or manganese dihalide; (Ix) a second material interspersed with said magnesium or manganese dihalide, which second material is capable of forming a reaction or addition product with an organic electron donor compound; and O 9 5 2 8 4 ~ * j W * / w a. w _ ^ 12.1.1983 59 225/18 (iii) a first organic donor-donor compound of which at least a portion reacts with at least a portion of said second pest to form a reaction product on at least the surface of said support, said support having a lower surface area than that by means of penetration having \ formed from said dihalide 'and second-called Peststoff ~ * product; and (b) exposing at least the surface of said support to a polymerization-active liquid titanium atomic charge to form a solid, titanium-containing catalyst component by binding of the titanium compound to at least the surface of said titanium-free catalyst support, the amount of titania exposed to the catalyst support and Amount of the located in the said catalyst component titanium correspond to each other substantially, or C) it is composed of (a) achieving comminution of a particulate material suitable for use in the alpha-olefin polymerization, together with a different, but substantially isostructural, particulate material to permeate said particulate material with said solid to form an intimate admixture; (b) subjecting the organic electron donor compound to said intimate admixture and reacting at least a portion of the said 0 9 52 8 - ^ - 59 225/18 said at least one portion of the surface of said intimate admixture to reduce the surface area of said intimate admixture to produce a catalyst support; and (c) exposing said catalyst support to a polymerization-active transition metal compound capable of being bonded to at least the surface of said catalyst support so as to form a solid catalyst component, the amount of transition metal compound present in said catalyst being substantially that amount of transition metal compound which has been exposed to said carrier in the preparation of said catalyst component, 2. The method according to item 1A, characterized in that said first particulate substance is selected from the group consisting of magnesium dihalides and manganese dihalides. -3. The method of item 2, characterized in that said titanium-free solid particulate catalyst carrier has a surface area of less than about 2 m / g. 4. The method according to item 3, characterized in that said first particulate matter is magnesium chloride, that the substantially solid material is aluminum trichloride with said isostructural second solid and said organic slektrone donor compound is anisole. 230952 8 -SA- 12.1.1983 "59 225/18 5. · -Verfahren.nach. Item 1B, characterized in that further the said titanium-free, solid, par-. ticular catalyst support of a second organic electron donor compound before, simultaneously with or after .the assembly with the said liquid titanium compound. wherein said second organic electron donor compound has been selected from those compounds capable of forming a reaction or addition product with said liquid titanium compound, and further, to exert no adverse effects on the polymerization , 6. Method according to item 1B or 5, characterized in that said magnesium or manganese dihalide has been permeated with said second pest before being exposed to said first organic electron donor compound · 7 »Method according to item 6, characterized in that. said magnesium or manganese dihalide and said second pest, which are both substantially isostructural, are comminuted together, then the mixture of the second solid interspersed with said magnesium or manganese dihalide is comminuted together with said first organic electron donor compound to produce one of Reaction conditions volatile reaction product is produced. 8. The method of item 1B, characterized in that said first electron donor compound by the possession of at least one functional group 23 O 9 5 2 8 - * L- 12.1. 59 225/18 which has been selected from among those organic functional groups capable of forming at least one volatile reaction product with said second pest under the conditions prevailing in the preparation of said catalyst component. Method according to item 5, characterized in that both said first and said
second organic electron donor compound selected from the group of those organic compounds
which contain at least one oxygen, sulfur, nitrogen or phosphorus atom, which is known as
Electron donor is able to act. 10. The method according to item 1C, characterized in that the transition metal compound is a
liquid titanium compound is. / f 11. The method according to item 10, characterized in that the steps of successive Sinwirkens by co-comminution of said Blektronendonatorverbindung with said intimate admixture
as well as subsequent common comminution of said liquid titanium compound with said titanium-free catalyst support, 12. The method according to item 10, characterized in that, moreover, after step (b) and before step (c), a common comminution of said titania-free catalyst support and a second organic electron donor compound takes place, wherein the molar ratio of said zv / eiter electron 23 0 9 52 8 - ^Ν 225/18 59 donor compound to said titanium compound = 1 or greater than List. 13. A method according to item 10, characterized in that said titanium compound is a liquid complex or a solid complex of a liquid titanium compound with a second organic electron donor compound, wherein the molar ratio of said zv / eiter electron donor compound to said liquid titanium compound is greater than 1 or j '.' 1 is » 14. T esteste; titaniumhaltige, suitable for use in the alpha olefin polymerization catalyst component, characterized in that A) it is produced by means of (a) forming a titanium-free, solid particulate carrier (i) subjecting a titanium-free particulate material suitable for use in alpha olefin polymerization to a substantially isostructural second pest to produce an intimate admixture or a solid solution; and (211) effecting an organic electron donor compound on said intimate admixture or solid solution under condition permitting at least a portion of said organic electron donor compound to react with said second plunger substance at least on the surface of said intimate admixture or solid solution to this way a titanium-free, solid, particulate 0 9 52 8 - * - 5S 225/18 To produce a spherical carrier, which has a smaller surface than the. having said intimate admixture or solid solution; and (b) exposing the said particulate carrier to a polymerization-active titanium compound capable of being bound at least on the surface of said carrier so as to form a solid, titanium-containing catalyst component having a surface area of less than about 1 m / g and wherein the amount of titanium in said catalyst component substantially corresponds to that amount of titanium which acted on said support in the preparation of said catalyst component, or B) it contains * (a) a core consisting of an intermixed admixture of first and second materials, said first material being selected from the group consisting of a magnesium dihalide or a hexane dihalide and suitable for use in alpha olefin polymerization, and the said second fabric has substantially the same structural configuration as said first fabric; (b) a reaction product at least on the surface of said core, said reaction product being formed in situ by a reaction between the second pest and a first organic electron donor compound during the comminution of said organic electron donor compound with the preformed core. 23 0 9 52 8 ~ 59 225/18 had been formed; (c) optionally, a second organic electron donor compound on said nucleus, said second electron donor compound being suitable for use in the polymerization of alpha olefins insofar as enhancing the steric regularity of the resulting polymer; and (d) a polymerisation-active transition metal formation which is present in a quantity equal to that mentioned y nucleus which substantially corresponds to that quantity of the transition metal compound which acted on said nucleus during the preparation of said catalyst component, said catalyst component being further characterized as having a specific surface area of less than 1m / g, C) it is composed of the reaction product Ci) of a hydrous, particulate, suitable for use in the alpha olefin polymerization support material and (ii) a dehydrating agent which is capable of reacting with the water in said catalyst support material to produce, under the given reaction conditions, a volatile reaction product and a substantially anhydrous catalyst support suitable for use in alpha olefin polymerization, said dehydrating agent is present only in an amount sufficient to react with water, which may exert a detrimental influence on the catalyst activity. 23 G 9 5 2 8 - 59 225/18 Solid catalyst catalyst according to item HS, characterized in that said first and second electron donor compounds were selected from the group consisting of organic compounds containing (i) at least one oxygen, sulfur, nitrogen or phosphodratotn which functions as an electron donating atom and which (ii) is characterized in that it comprises at least a fraction of those organic constituents which produce at least one readily volatile reaction product with said second substance under the conditions prevailing in the preparation of said catalyst component. » A solid catalyst component according to item 15, characterized in that said second solid selected from aluminum trihalides, said first slektrone donor compound is selected from the arylalkyl ethers, said second nickel electrogen compound is selected from alkyl carboxylic acid esters and said polymerization-active transition metal compound is selected from titanium tetrahalides, A solid catalyst compound according to item 15, characterized in that said first and second materials are magnesium dichloride and aluminum trichloride, that said first and second electron donative compounds are methyl phenyl ether and ethyl benzoate, and that said said polymerization-active transition metal compound is titanium tetrachloride. 23 0 9 52 8 '*? ™ £% 18. A catalyst carrier according to item 14C, characterized in that said dehydrating agent is selected from the group consisting of the silicone tetrahalides, calcium hydride and calcium carbide. 19 · Catalyst support according to item 18, characterized in that the said dehydrogenating agent is silicon tetrachloride * Berlin, 12. 12. 1981 C 08 P / 230 952/8 23 0 9 5 2 8 ~ ^ή ' ^{5S 225 18} Process for the preparation of a catalyst support Field of application of the invention The invention "relates to a process for the preparation of a catalyst support * In particular, the invention is directed to a highly effective "supported catalyst" for the production of polyols. finen * Characteristic of the known technical solutions Organometallic compounds have been used in combination with transition metal compounds to catalyze the production of high molecular weight ethylene and alpha olefin polymers and, in turn, to produce polymers of high steric regularity when employed. ,. The hasic catalysts used in these processes are formed by combining a transition metal salt with a metal alkyl or hydride. Often, titanium trichloride and an aluminum alkyl such as triethylaluminum or diethylaluminum chloride are used. However, such catalysts generally have a low productivity and form only polymers with a low steric regularity. Isotactic polypropylene arises from a head-to-tail concatenation of the monomer units, as a result of which all asymmetric carbon atoms have the same configuration - ρ -