DE2739608A1 - METHOD FOR PRODUCING ALPHA OLEFIN POLYMERS OR COPOLYMERS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmanr - Dr. R. Koenigsoerger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. K | ir.qse; sen - Dr. F. Zumstein jun.

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Process for the production of α-olefin polymers or -copoly-

meren

The invention "relates to an improved process for the preparation of α-olefin polymers or copolymers having improved stereoregularity and bulk density with improved catalytic activity by polymerization or copolymerization of cc-olefins having at least 3 carbon atoms or copolymerization of α-olefins having at least 3 carbon atoms with ethylene in two stages under special conditions in the presence of a catalyst consisting (a) a solid titanium catalyst component (a) consisting essentially to the magnesium, titanium, halogen and an electron donor, and (B) an organometallic compound of a metal of groups I to III of the Periodic Table of the Elements.

It is known that a catalyst which (A) is a solid titanium

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complex catalyst component, (A) consisting essentially of Magnesium, titanium, halogen and an electron donor, and (B) an organometallic compound of a Group I metal to III of the Periodic Table of the Elements for the preparation of α-olefin polymers or copolymers with good stereoregularity with superior catalytic activity is suitable and a number of recommendations have been made for use the solid titanium complex catalyst components (A) made from various combinations of catalyst-forming components and / or made under special combinations of catalyst-forming combinations (e.g. DT-OS 22 30 728, corresponding to Japanese Patent Publication 16986/73 and FR-PS 2 143 347; DT-OS 23 47 577, corresponding to the JA patent publication 86462/7 ^, GB-PS 1 435 768 and FR-PS 2 200 290, DT-OS 25 04 036, corresponding to the JA patent publications 108385/75 and 20297/76, and FR-PS 2 259 842; DT-OS 25 53 104, corresponding to the JA patent publication 126590/75; HL-PS 7510394, corresponding to the JA patent publication 28189/76 and FR-PS 2 283 909; JA patent publication 57789/76; JA Patent Publication 64586/76; DT-OS 26 05 922, corresponding to JA patent publication 92885/76, JA patent publication 127185/76 and JA patent publication 136625/76).

So far, however, there has been no positive recommendation about a two-stage Polymerization process using the catalyst component (A), since the two-step process is obvious-Ii ch disadvantageous compared to a one-step process in industrial Is working method and no benefit is to be expected from a two-step process that compensates for this disadvantage would.

Some recommendations regarding a two-stage polymerization of propylene with common catalysts of the titanium trichloride type, such as a titanium trichloride composition obtained by reducing titanium tetrachloride with metallic aluminum or other reducing agents are known (for example

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JA patent publication 32312/72, JA patent publication 14865/74 and GB-PS 1,359,844 corresponding to JA patent publication 2439/72). However, it is known that in the polymerization of propylene using these common titanium trichloride type catalyst components other than the above catalyst component (A), the use of high reaction temperatures in an attempt to increase the polymerization activity lowers the crystallinity of the polymer and vice versa Use of low temperatures in the reaction in an attempt to increase crystallinity inevitably leads to decreased polymerization activity of the catalyst. Therefore, in view of the balance between the polymerization activity and the crystallinity, temperatures of about 60 to about 70 ° C. are most suitably used for the polymerization of propylene. It has been found that in the polymerization of propylene with these usual catalyst components of the titanium trichloride type at about 60 to 70 ⁰ C there is essentially no difference in the result between a one-stage polymerization process and a two-stage polymerization process in which a polymerization in the first stage at low temperature and a polymerization in the second stage at about 60 to 70 ⁰ C is carried out. Essentially, the amount of polymer formed per unit weight of catalyst per unit time is essentially the same for both processes, and in the case of a batch reaction, the proportion of stereoregular polymer formed and the bulk density of the polymer are essentially the same for both or somewhat in the two-step process higher. Accordingly, there is no apparent significant advantage for using the two-stage procedure while accepting the disadvantage of implementation.

Carrying out the second stage of two-stage polymerization process using conventional Titantrichloridkatalysatorkomponente at a temperature in excess of about 80 ⁰ C

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by, so tend to the amount of polymer formed that Bulk density of the polymer and the yield of a highly stereoregular polymer lead to a reduction, for example by the experiments in the aforementioned JA patent publication 14865 / 74- can be seen. The use of such higher temperatures is not practical.

Attempts have now been made to achieve improved results in the polymerization or copolymerization of α-olefins having at least 3 carbon atoms, the copolymerization of α-olefins with at least 3 carbon atoms with ethylene, preferably with "up to 10 mol percent ethylene, or the copolymerization of these oc-olefins with dienes (these are sometimes used for simplicity as polymerization or copolymerization of α-olefins with at least 3 carbon atoms) using a solid titanium complex catalyst component (A) which consists essentially of magnesium, titanium, halogen and an electron donor, which are different from the usual types of Titanium trichloride catalyst components differentiate to achieve. It has now been found, surprisingly, that the Use of a two-stage polymerization process with of the catalyst component (A) under special conditions to an improved catalytic activity and stereoregularity and an increased bulk density.

It has also been found that when using the catalyst component (A) in the above two-stage polymerization process with the usual titanium trichloride catalyst, the second stage being carried out at about 60 to 70 ^° C., within this temperature range there is no significant improvement in the use of the method disadvantageous two-stage process in comparison with the one-stage process is evident, a considerable improvement in the catalyst activity is obtained, which is completely unexpected with regard to the one-stage polymerization. These unexpected results cannot be avoided

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the results can be derived from the two-stage. Polymerization process using conventional titanium trichloride catalysts achieved.

It was also found that inclines at a polymer ions temperature of at least 7O ° C, for example about 80 ⁰ C at which decrease the amount of crystalline polypropylene, the reaction mixture can be prevented due to the increase of the amount of amorphous polymers viscous to and a substantial reduction in the yield of the polymer can also be avoided.

You excellent results obtained by the process according to the invention using the catalyst component (A) are not derived from the results of the two-stage polymerization process with conventional titanium trichloride catalysts expected.

The subject of the invention is therefore the provision of a considerably improved process for the polymerization or copolymerization of ct -olefins having at least 5 carbon atoms in two stages.

The foregoing and many other objects and advantages of the invention will be apparent from the description below.

According to the invention, a process for the production of α-01efin polymers or copolymers by polymerization or copolymerization of <x-01 efins with at least 3 carbon atoms at tree temperature or a higher temperature under a pressure of about 1 to 100 kg / cm ² in the presence of a catalyst is created which comprises (A) a solid titanium complex catalyst component consisting essentially of magnesium, titanium, halogen and an electron donor, and (B) an organometallic compound of a metal of

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Groups I "to III of the Periodic Table of the Elements, such as one Alkylaluminum compound, being the polymerization or copolymerization is carried out in two stages:

(a) a first stage, "in which at least about 100 millimoles per millimole of titanium atom of an a-01efins" is polymerized at a temperature of less than about ^ 0 ⁰ C to form a polymer or copolymer, its amount not above about 50 weight percent that of the end product, which is obtained in the second stage, and

(b) a second stage, "in which the final product bit at a temperature above the temperature of the first stage and from about 50 about 90 ⁰ C is formed.

The solid complex titanium component (A) is obtained by intimately contacting a magnesium compound (or magnesium metal), a titanium compound and an electron donor by means such as heating or copulverization. The solid complex has a halogen / titanium molar ratio greater than about 4 and does not substantially allow the release of a titanium compound upon washing with hexane at room temperature. The chemieche structure of this solid complex is not known, but are probably the o'e- ^v Magne Situ atom and the titanium atom feet tied, for example, in that they have the halogen atom in common. Depending on the production method, the solid complex can contain a further metal atom, such as aluminum, silicon, tin, boron, germanium, calcium and zinc, an electron donor or a corresponding organic group. It can also contain an organic or inorganic inert diluent such as LiCl, CaCO ,,

, Na ₂ CO ₅ , SrCl ₂ , B ₃ O ,, Na ₃ SO ₄ , Al ₃ O ₅ , SiOg, TiO ₃ , NaB ₄ O ₇ , Caj (P0 ₄ ) ₂ , CaSO ₄ , Al ₂ (SO ₄ J ₅ , CaCl ₂ , ZnCl _31, polyethylene, polypropylene and polystyrene. Preferably, the solid complex is one treated with an electron donor. In preferred examples of the solid complex titanium

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component (A) the halogen / titanium molar ratio is above about 4, preferably "at least about 5, particularly" preferred at least about 8, and the magnesium / titanium molar ratio Uegb "at least about 3, preferably about 5 to about 50, and that Electron donor / titanium molar ratio "at about 0.2 to about 6, preferably about 0.4 to about 3, more preferably about 0.8 to about 2. In addition, the specific surface area of the solid is at least 3 m / g »preferably at least

at least about 40 m / g and particularly preferably at least about

100 m / g. It is also desirable that the X-ray spectrum of the solid complex (A) shows an amorphous character regardless of the parent magnesium compound or in one is more amorphous than commonly available types of magnesium dihalide.

The solid titanium complex catalyst component (A) can be prepared by a procedure known per se. These procedures are, for example, in those above with respect to the use of a solid titanium complex catalyst component (A) mentioned patents, as well as in the JA patent publications 4056/76, 16489/76, 21179/76, 63536/76, 76085/76 and 114836/76.

Examples of methods described in these references are, include the reaction of at least one magnesium compound (or of metallic magnesium), one Electron donor and a titanium compound.

Examples of the electron donor are oxygen-containing Electron donors such as water, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, ethers and acid amides, and nitrogen containing electron donors such as ammonia, amines, nitriles and isocyanates.

Specific examples of such electron donors include alcohols having 1 to 18 carbon atoms, such as methanol,

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Ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropyrbenzyl alcohol; Phenols having 6 to 15 carbon atoms which may contain a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol and naphthol; Ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthoaldehyde; organic acid esters with 2 to 18 carbon atoms, such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl acetate, methyl methacrylate, octyl crotonate, methyl benzoyl benzoate, propyl benzoylate, methyl methacrylate, octyl crotonate, methyl benzoyl benzoate, butyl benzoyl benzoate, butyl benzoyl benzoate, butyl benzoyl benzoylate, butyl benzoyl benzoate, octyl acetate, cyclohexyl , phenyl benzoate, benzyl benzoate, methyl toluate, Äthyltoluat, Amyltoluat, Äthyläthylbenzoat, methyl, Äthylanisat, Athyläthoxybenzoat,) -ButyrοIacton, valerolactone, coumarin, phthalide and ethylene carbonate; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluic acid chloride and anisic acid chloride; Ethers with 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; Acid amides such as acetamide, benzamide and toluamide; Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile and tolunitrile; and compounds of aluminum, silicon, tin, etc. containing the above functional groups in the molecule. These electron donors can be used as a mixture of two or more.

Suitable magnesium compounds which are used to form the solid complex titanium compound (A) are those which contain halogen and / or organic groups. Specific

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Examples of such magnesium compounds include magnesium dibalides, Magnesium alkoxyhalides, magnesium aryloxybalogenides, Magnesium hydroxyhalides, magnesium dialkoxides, Magnesium diaryloxide, magnesium alkoxyaryloxide, magnesium acyloxyhalide, magnesium alkylbalogenide, magnesium aryl halide, Magnesium dialkyl compounds, magnesium diaryl compounds and magnesium alkyl alkoxides. They can be in the form of adducts with the above electron donors. They can also be double compounds that contain other metals, such as aluminum, tin, silicon, germanium, Zinc or boron. For example, they can be double compounds of halides, alkyl compounds, alkoxy halides, aryloxy halides, Be alkoxides and aryloxides of metals, such as aluminum and the magnesium compounds mentioned above as examples. They can also be double compounds in which phosphorus or boron is bound to magnesium via oxygen is. These magnesium compounds may be a mixture of two or more. Usually the above Examples of compounds are represented by simple chemical formulas, but sometimes they can vary cannot be expressed by simple formulas after the magnesium compounds have been prepared. You will in general considered as mixtures of the above compounds. For example, compounds are obtained by a method which consists in combining magnesium metal with an alcohol or phenol in the presence of a halosilane, of Phosphorus oxychloride or thionyl chloride and by a method which consists in pyrolyzing Grignard reagents or to decompose them with compounds that have a hydroxyl group, a carbonyl group, an ester bond, an ether bond or the like, as mixtures of various compounds depending on the amounts of the reagents or the extent of the reaction considered. These compounds can of course be used according to the invention.

There are several methods of making the above

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magnesium compounds mentioned as examples are known, and products of any of these methods can be used in the present invention will. Also, before use, the magnesium compound can be treated, for example, by a method that includes consists in dissolving them alone or together with another metal compound in ether or acetone and then the To evaporate the solvent or to introduce the solution into an inert solvent and thereby deposit the solid. A method can also be used which consists of adding at least one magnesium compound with or without mechanically pre-powdering any other metal compound.

Preferred among these magnesium compounds are magnesium dihalides, aryloxyhalides and aryloxides and double compounds of these with aluminum, silicon, etc. In particular, they are MgCl ₂ , MgBr ₂ , MgJ ₂ , MgF ₂ ,)

_{652 6} ^ _{3 6452} (MgCl ₂ ) _x CAl (OR) _n Cl ₃ _ _n 3 _y and (MgCl ₂ ) _χ [Si (OR) ^ I _4- J ₇ . In these formulas, R represents a hydrocarbon group such as an alkyl or aryl group, and m or η groups R are the same or different and 0 S η 5 2, OSmS 4, and χ and y are positive numbers. MgCl ₂ and its complexes or double compounds are particularly preferred.

Suitable titanium compounds which are used to form the solid complex titanium compound (A) are tetravalent titanium compounds of the formula Ti (OR) X ₄ , wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms, X is a halogen atom and 0 = g = 4. Examples of the titanium compounds are titanium _{tetrahalides, such as TiCl 4} , TiBr ₄ or TiI ₄ ; Alkoxytitanium trihalides such as Ti (OCH ₅ ) Cl ₅ , Ti (OC ₂ H ₅ ) Cl ₅ , Ti (O ^ C ₄ H ₉ ) Cl ₅ , Ti (OC ₂ H ₅ ) Br _5, and Ti (O ISO-C ₄ HQ) Br ₅ ; Alkoxy titanium dihalides such as Ti (OCH ₃ ) ₂ C1 ₂ , Ti (OC ₂ H ₅ ) ₂ C1 ₂ , Ti (O HC ₄ Hg) ₂ Cl _2, and Ti (OC ₂ H ₅ ) ^ r ₂ ; Trialkoxy

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titanium monohalides such as Ti (OCH ₅ ), Cl, Ti (OCpH ₅ ), Cl, Ti (O nC) Cl, and Ti (OC ₂ Hr) ₃ Br; and tetraalkoxy titanium, such as Ti (0CH ₅ ) ₄ ,

and Ti (O nC ^ H _Q ) ₄ . Among them, the titanium tetrahalides are preferred, and particularly preferred is the titanium tetrachloride.

There are various examples of the implementation of the magnesium compound (or metallic magnesium), the electron donor and the titanium compound for preparing the titanium complex catalyst component (A), and typical thereof are im listed below:

I) A method involving the reaction of the magnesium compound with the electron donor and subsequent reaction of the reaction mixture with the titanium compound: I-a) Method I) with copulverization of the magnesium compound and the electron donor:

The electron donor added at the time of copulverization need not be in the free state and be in the form of an adduct with the magnesium compound. To the At the time of co-pulverization, additional constituents may be present at the same time that are present in the complex titanium component

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Α) can be included, for example the one mentioned above organic or inorganic inert diluents, a halogenating agent such as a halogen compound of silicon, a silicon or silicone compound, such as polysiloxane, a compound of aluminum, germanium or tin or part of the titanium compound. The electron donor can also be in the form of an adduct (complex compound) with such an adduct Connection. The amount of the electron donor used is preferably from about 0.005 to about 10 moles, particularly preferably from about 0.01 to ~ 1 mole per mole of the magnesium compound.

The copulverization can be carried out using conventional devices such as a rotary ball mill, a vibratory ball mill, and an impact mill. When using the rotary ball mill, 100 stainless steel (SUS 32) balls with a diameter of 15 mm are placed in a ball mill cylinder with an inner fit of 800 ml and an inner diameter of 100 mm made of stainless steel (SUS 32) and 20 to 40 g of the materials to be treated are introduced and it is advisable to carry out pulverization for at least 24 hours, preferably at least 48 hours at a speed of rotation of 125 rpm. The temperature of the pulverization treatment is usually from room temperature to about 100 ^° C.

The copulverized product can also be reacted with the titanium compound by copulverization. However, it is preferred to suspend the copulverized product in at least about 0.05 moles, preferably about 0.1 to about 50 moles per mole of the magnesium compound of a liquid titanium compound with or without an inert solvent without copulverization. The reaction temperature is from room temperature to about 200 ^° C. and the reaction time is from 5 minutes to about 5 hours. The reaction can of course also be carried out under conditions which are outside these specified ranges. After the reaction, the reaction mixture becomes hot

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a high temperature of about 60 to 150 ⁰ C filtered in order to isolate the product, which is then washed well with an inert solvent before the polymerization.

I-b) Method I) without copulverization of the magnesium compound and the electron donor:

Usually, the magnesium compound is reacted with the electron donor in an inert solvent, or the magnesium compound is dissolved or suspended in the liquid electron donor for reaction. It is possible to use an embodiment in which magnesium metal is used as a starting material and is reacted with the electron donor to form a magnesium compound. The amount of electron donor used is preferably from about 0.01 to about 10 mol, particularly preferably from about 0.05 to about 6 mol per mol of the magnesium compound. The reaction proceeds sufficiently at a reaction temperature from room temperature to about 200 ^° C. for 5 minutes up to about 5 hours. After the reaction, the reaction mixture is filtered or evaporated and washed with an inert solvent to isolate the product. The reaction of the reaction product with the titanium compound can be carried out in the same way as described in Ia).

I-c) A process which consists in the reaction product to react between the magnesium compound and the electron donor with a compound which is selected from organoaluminum compounds, silicon or silicone compounds and tin compounds and subsequent reaction of the resulting product further with the titanium compound: This process is a special embodiment of procedure I-b). In general, complexes show that the method I-a) were obtained, superior business on and some of the complexes obtained by method I-b) th have inferior properties than those obtained by method I-a). The properties of such

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Complexes can be improved very effectively by performing method I-c), in which the organoaluminum compound, Silicon compound or tin compound is reacted with the titanium compound before the reaction.

Examples of the organoaluminum compounds used in this Method that can be used are trialkylaluminum compounds, Dilalkylaluminum hydrides, dialkylaluminum halides, Alkyl aluminum sesquihalides, alkyl aluminum dihalides, Dialkyl aluminum alkoxides or phenoxides, alkyl aluminum alkoxyhalides, or phenoxyhalides and mixtures thereof. Among these are the sialkyl aluminum halides, alkyl aluminum sesquihalides, Alkyl aluminum dihalides and mixtures thereof are preferred. Specific examples of these include triethylaluminum, Trii sobutyl aluminum, diethyl aluminum hydride, Dibutyl aluminum urahydride, diethyl aluminum chloride, diisobutyl aluminum bromide, Ethyl aluminum sesquichloride, ethyl aluminum ethoxide, ethyl aluminum ethoxychloride, ethyl aluminum dichloride and butyl aluminum dichloride.

You silicon or tin compounds, for example silicon or tin halogen compounds or organic compounds are compounds that contain at least one halogen or hydrocarbon group contain bonded directly to silicon or tin and may further contain hydrogen, an alkoxy group, a phenocyan group. or similar. Specific examples include Silicon tetrahalides, tetraalkyl silicon compounds, Silicon alkyl halides, silicon alkyl hydrides, tin tetrahalides, Tin alkyl halides and tin hydride halides · Among these bind silicon tetrachloride and tin tetrachloride preferred.

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The reaction of the resulting reaction product between the magnesium compound and the electron donor with the organotium compound, silicon compound or tin compound can be carried out in an inert solvent. Such a compound is used in an amount of preferably about 0.1 to about 20 moles, preferably about 0.5 to about 10 moles per mole of the magnesium compound. The reaction is preferably carried out at a temperature from room temperature to about 100 ^° C. for 5 minutes to 5 hours. After the reaction, the reaction mixture is preferably washed well with an inert solvent and then reacted with the titanium compound. The reaction of this reaction product with the titanium compound can be carried out according to the method described under Ia) '.

II) A process which consists in simultaneously using the magnesium compound, to implement the electron donor and the titanium compound.

III) A process which consists in using the reaction product of the titanium compound and the electron donor with the magnesium compound to implement.

The reactions of these methods II) and III) are preferably carried out by co-pulverizing. The pulverization conditions and the proportions of the starting materials are the same as described under method I). In these methods however, it is not preferable to use a large amount of the titanium compound. The amount of titanium compound is preferably from about 0.01 to about 1 mole per mole of the magnesium compound. .

The above methods are exemplary methods, and many modifications are possible as shown below.

1) The method I) in which the electron donor is present when the titanium compound is reacted.

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2) A method in which the organic or inorganic inert diluent and the silicon, aluminum, germanium or tin compounds are present during the reaction; a method of making these compounds prior to implementation to be allowed to work; a method by which these connections between reactions are brought into effect will; a method in which these compounds are brought into action after the reaction. Case in point for methods is method I-c). These reagents can be used at desired points in the above methods will.

For example

2-a) a method in which a halogenating agent such as SiCl. to act on the compound obtained by methods I), II) and III).

5) A method in which the titanium compound. Two or more times is brought to action:

3-a) The method in which the titanium compound and the electron donor be reacted with the reaction product which is obtained by one of methods I) to III). 3-b) The method in which the titanium compound, the organoaluminum compound and the electron donor are reacted with the reaction product of one of the methods I) to III).

by

A number of other modifications can / change the order adding the reagents or performing a plurality of reactions or using additional ones Reactants are carried out. In any of these methods it is beneficial to have halogen, titanium and magnesium in the complex A), the proportion of the electron donor, the surface of the complex A) and the X-ray spectrum of the catalyst are within the above ranges or conditions.

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Examples of the electron donor which is favorably incorporated into the catalyst component (A) are esters, Ethers, ketones, tertiary amines, acid halides and acid anhydrides, which do not contain active hydrogen. Organic acid esters and ethers are particularly preferred and most preferred are aromatic carboxylic acid esters and alkyl containing ethers. Typical examples of suitable aromatic carboxylic acid esters include lower alkyl esters such as lower alkyl esters of benzoic acid and lower alkyl esters of alkoxybenzoic acid. The term "low" means the content of 1 to 4 x carbon atoms. Those having 1 or 2 carbon atoms are particularly preferred. Suitable alkyl-containing ethers are those containing 4 to 20 carbon atoms, such as diisoamyl ether and dibutyl ethers.

The organometallic compound b) has a hydrocarbon group directly bonded to the metal and includes, for example, alkyl aluminum compounds, alkyl aluminum alkoxides, alkyl aluminum hydrides, alkyl aluminum halides, alkyl zinc compounds and dialkyl magnesium compounds. Preferred among them are the organoaluminum compounds. Specific examples of the organoaluminum compounds are trialkyl or trialkenyl aluminum compounds such as Al (C ₂ Hc) ₅ , Al (CH ₃ J ₃ , Al (C ₃ H ₇ J ₃ , A1 (C ₄ H ₉ ) ₃ and Al (C ^ H ₂₅ J ₃ ; alkyl aluminum compounds with a structure such that many aluminum atoms are linked by oxygen or nitrogen atoms, such as (C ₂ H ₅ ) ₂ A1OA1 (C ₂ H ₅ J ₂ , (C ₄ Hg) ₂ AlOAl (C ₄ H ₉ J ₂ and (C ₂ H ₅ ) ₂ A1NA1 (C ₂ H ₅ J ₂ ;

^C 6 ^H 5
Eialkylaluminum hydrides such as (C ₂ H ₅ J ₂ AlH or (C ₄ H ₉ J ₂ AlH; dialkyl

aluminum halides such as (C ₂ H ₅ J ₂ AlCl, (C ₂ H ₅ J ₂ AlI or (C ₄ H ₉ J ₂ AlCl and dialkyl aluminum alkoxides or phenoxides such as (C ₂ H ₅ J ₂ Al (OC ₂ and (C ₂ H ₅ J ₂ Al (OC ₆ H ₅ ). Of these, the trialkylaluminum compounds are most preferred.

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Preferably the organometallic compound (B) is used together with an electron donor (C) used, "for example, those above with respect to the catalyst component (A) as Examples given. Above all, it is preferably used together with an organic acid ester, particularly an aromatic one Carboxylic acid esters with 8 to 18 carbon atoms, such as methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-toluate, Methyl p-anisate and ethyl p-anisate are used. One of those organic carboxylic acid ester serves to keep the yield of highly stereoregular polymer at a high level, even if the polymerization is carried out in the presence of hydrogen.

The titanium complex catalyst component (A), the organometallic compound (B) and the electron donor (C), preferably the organic carboxylic acid, can be mixed in any order desired. The appropriate amount of the free organic carboxylic acid ester is not more than 1 mol, preferably about 0.01 to 0.5 mol per metal atom of the organometallic acid Link.

According to the method of the invention, α-01efine with at least 3 carbon atoms polymerized or copolymerized in the presence of a catalyst comprising (A) the solid Titanium complex catalyst component, consisting essentially of magnesium, titanium, halogen and an electron donor, and (B) the organometallic compound of a metal from Groups I to III of the Periodic Table of the Elements with or without (C), the electron donor.

The polymerization temperature in the first stage is not higher than about 50 ^° C. However, in view of the removal of the heat of polymerization or the rate of polymerization, too low a temperature is not preferred. Usually the temperature is above room temperature. The amount of α-olefin polymerized in the first stage is at least about 100 millimoles, preferably at least about

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1000 hillimoles per millimole of titanium atom in the titanium complex catalyst component (A). There is no specific upper limit on the amount of ot-olefin polymerized. the The rate of polymerization increases with the increasing amount of α-olefin that polymerizes in the first stage however, beyond a certain point the rate of polymerization tends to decrease again. The amount to be polymerized in the first stage is greater than that a-01efins does not exceed about 30 percent by weight of the final product finally obtained in the second stage

In the first polymerization stage, it is preferred to use a das Molecular weight controlling agent, preferably hydrogen. The amount of hydrogen added is from about 0.3 to about 40 moles, in particular from about 4 to about 20 moles Mol percent based on the oc-olefin.

After the first polymerization, the temperature is raised and the second stage polymerization is carried out at a temperature which is above the temperature of the first polymerization step, preferably at least 10 ° 0 is above the temperature of the first polymerization stage, at preferably about 50 to 90 ⁰ C, especially preferably about 60 to 80 ^° C. If the temperature rises above about 90 ^° C., both the catalytic activity and the bulk density and the proportion of the stereoregular polymer formed tend to decrease.

In the second polymerization stage, too, the molecular weight of the polymer is preferably adjusted using hydrogen.

There is no particular limitation on the polymerization pressure. Preferably, however, the polymerization pressure is in the first stage of roughly atmospheric

Pressure up to about 20 kg / cnr and the polymerization pressure in the

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second stage from atmospheric pressure to about 50 kg / cm.

Preferred cc-olefins are those containing at least 3 carbon atoms contain, such as propylene, 1-butene and 4-methyl-1-pentene. The polymerization can be a homopolymerization or Be copolymerization. As a comonomer up to 10 Mole percent ethylene can be used. Dienes can also be used as comonomers.

In the usual copolymerization of propylene with ethylene the bulk density of the polymer tends to suddenly decrease with increasing ethylene content in a one-step process to become. However, the two-step process according to the invention makes it possible to produce a polymer with a high Obtain bulk density. Even with homopolymerization an improvement in the bulk density and the proportion of the stereoregular polymer formed is achieved and observed a considerable increase in the amount of polymer formed per unit weight of catalyst per unit time. No justification is apparent for the unexpected result of the increased catalyst activity, but it is believed to be a feature of that used in the present invention Catalyst is.

The following examples serve to illustrate the invention.

Example 1 Preparation of a catalyst (component A)

20 g of commercially available anhydrous magnesium chloride, 6.0 ml Ethyl benzoate and 3.0 ml of silicon tetrachloride were placed in a ball mill cylinder under a nitrogen atmosphere stainless steel (SUS 32) with an internal capacity of 800 ml and an inner diameter of 100 mm, the 100 stainless steel balls (SUS 32) with a diameter of 15 mm and contact was made for 48 hours at 125 rpm

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held.

The solid product obtained by the treatment was suspended in 150 ml of titanium tetrachloride. The solid material was recovered by filtration and washed with purified hexane until no more free titanium tetrachloride in the washing liquid could be determined, component (A) being obtained which contained 1.6 percent by weight of titanium, 64.0 as atoms Weight percent chloride and 8.9 weight percent ethyl benzoate.

Polymerization

An autoclave with an available volume of 2 liters was charged with 1.0 liter of kerosene, 1.8 millimoles of triethylaluminum, 0.6 millimoles of ethyl benzoate and 0.1 millimoles, calculated as titanium atom, of the catalyst component (A) obtained above . 250 ml of hydrogen were added and the system was kept at 40 ^° C. for 10 minutes by charging with propylene at an overpressure of 4 kg / cm. About 40 g of propylene was polymerized in this way. The temperature of this system was then raised to 60 ^° C. in the course of about 20 minutes and propylene was continuously fed in and polymerized for 20 hours at an excess pressure of 7.0 kg / cm. The solid material was collected by filtration, washed with hexane and dried to obtain 486 g of polypropylene as a white powder. The powdery polypropylene had an extraction residue of 96.4% in boiling n-heptane, a bulk density of 0.42 g / ccm and a value of [72] of 2.9. Furthermore, by concentrating the liquid layer, 14.3 g of a soluble polymer was obtained.

Examples 2 and 3

Propylene was polymerized using the same catalyst and polymerization procedure as in Example 1, however, the amount of polymerized product

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pylens in the first stage as shown in Table I. The results are shown in Table I below.

Table I.

Amount of Polymeri Amount of Backlog lot 2.7 Schütt Propylene, station finally in simmer - at 2.9 density loaded time i.d. get to the Losli At- in which he first a poly n-heptane chem Po sp. first level step meren lymeren (G) (Minutes) (G) (%) (g / ccm) 2 IO 3 474 95.2 12.5 0.42 3 125 4o 536 95.6 14.7 0.43

Example 4

Propylene was polymerized using the same catalyst and the same polymerization process as in Example 1, except that the polymerization in the second stage was ^{carried out at 70 °} C. and the amount of hydrogen added was changed to 150 milliliters. 523 g of polypropylene were obtained as a powder with an extraction residue in boiling n-heptane of 95.8%, a bulk density of 0.38 g / ccm and a value for L 1 of 2.6.

By concentrating the liquid layer, 17.3 g of a soluble polymer was obtained.

Comparative experiments 1 and 2

Propylene was polymerized for 2.5 hours at 6O ⁰ C or 70 ⁰ C using the same catalyst and the same polymerization procedure as in Example 1, but with the

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! .5

first stage was omitted. The amount of hydrogen added was changed to 150 milliliters, when the temperature reached -70 ^Q C. The results are shown in Table JI along with the results of Example 1.

Table II

Ver
equal
attempt Polymeri
station
tempera-
door
( ⁰ C) Poly
propylene
powder
(ε) Extra
ions
Residue
in her
end
n- ^ ptan soluble
Polymer
(G) Schütt
density
(g / ccm) O) J- 60
70 (»12
422 92.2
91.3 16.3
17.4 0.37
0.33 2.6
8.6 Beep. 1 486 96.4 14.3 0.42 8.9

The results show that when the first stage was carried out there was an obvious increase in bulk density and stereo regularity compared with the case where the first stage was omitted. Surprisingly, the amount of polymer formed per unit weight of the catalyst increased considerably. This clearly represents the benefit of the first stage treatment.

Deterioration attempt 3

This experiment illustrates the implementation of the polymerization in the first stage with a conventional catalyst of the titanium trichloride type.

Polymerization

An autoclave with an available volume of 2 liters was made

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charged with 1.0 liter of kerosene, 6.0 millimoles of diethylaluminum chloride and 2.0 millimoles of titanium trichloride (grade AA). 400 ml of hydrogen were added and about 27 g of propylene were polymerized, propylene being ^{fed in for 20 minutes at 40 °} C. and an overpressure of 4 kg / cm.

The temperature of the system was then raised to 70 ^° C. in the course of 20 minutes and propylene was continuously fed in and polymerized for ^{4.0 hours at 7.0 kg / cm 2 overpressure.}

For comparison, the polymerization was carried out at 70 ^° C. for 4 hours and 40 minutes without carrying out the first polymerization stage. The results are shown in Table III.

Polypro
pylen
powder
(G) Table III soluble
ches
Poly
meres
(G) Schütt
density
(g / ccm) 2.9
3.0 452
436 52.0
41.4 0.37
0.39 Perform
tion of the
first
step Extraction
Residue
in simmer
the n-Hep
tan _(%) no
aa 97.1
96.5

The results show that there is little effect of the first stage polymerization on the increase in bulk density and the Stereoregularity could be determined. However, the effect was much less than the effect with the one on one Supported catalyst of the titanium tetrachloride type and it can be seen that the effect of the first stage is essentially is not found with the usual catalyst. A comparison of Table II with Table III shows that

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the application of the two-stage procedure has a unique effect with that containing a titanium catalyst component Catalyst results.

Example 5

This example illustrates the effect of the first polymerization stage on the random or Handom copolymerization of propylene and ethylene in the presence of the catalyst in the table I.

Polymerization

An autoclave with an available volume of 2 liters was made with 1.0 liter of kerosene, 1.8 millimoles of triethylaluminum, 0.42 Millimoles of ethyl benzoate and 0.1 millimoles, calculated as titanium atom, of the catalyst component (A) obtained in Example 1, loaded. 150 milliliters of hydrogen were added and about 15 g of propylene were polymerized, with propylene at 40 ° 0 fed in for 10 minutes and at 2 kg / cm excess pressure became.

The temperature of the system was then raised to 60 ^° C. over the course of 20 minutes and propylene gas, which contained 5.7 mol percent ethylene, was fed in continuously and polymerization was carried out for 2 hours at 5.0 kg / cm excess pressure.

For comparison purposes, propylene gas with a content of 5.9 mol percent ethylene was fed in continuously and at 60.degree polymerized for 2.5 hours, but the first polymerization stage at 40 ° C was not carried out.

The results are shown in Table IV.

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-, 26 -

Is

Table IV

execution
•the first
step powder feed
middling copo
polymer s (g) Soluble
Polymer
(β) Bulk density
(g / ccm) (η) no
(Comparison)
there
(required acc.) 299
482 57
58 0.27 2.7
2.6

The results show that the ratio of soluble polymers to the powdery copolymer was lower and the bulk density of the polymer was higher when the first was carried out Stage in comparison without carrying out the first stage. The effect was greater than in the case of homopolymerization.

Example 6 Preparation of Catalyst Component A

0.1 mol of commercially available anhydrous magnesium chloride was suspended in 0.3 liter of kerosene and 0.4 mol of ethanol and 0.1 mol of ethyl benzoate were added to the suspension at room temperature. Then 0.3 mol of diethyl aluminum chloride was added at room temperature and the mixture was stirred for one hour. The solid portion of the product was recovered, sufficiently washed with kerosene, suspended in 0.3 liter of kerosene solution containing 30 milliliters of titanium tetrachloride and transferred for 2 hours at 8O ⁰ C for reaction. After the reaction, the supernatant liquid was removed by decantation and the solid portion was carefully washed with fresh kerosene. The resulting solid contained 423 mg of titanium, 582 mg of chlorine and 132 mg of ethyl benzoate on an atomic basis.

Polymerization

An autoclave with an available volume of 2 liters was made

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with 1.0 liter of kerosene, 1.6 millimoles of triethylaluminum and 0.5 Millimoles of ethyl benzoate and 0.07 millimoles, "calculated as titanium atom, the catalyst component (A) prepared as described above is charged. 250 milliliters of hydrogen were added and about 35 g of propylene were fed with propylene at 40 ° 0 and 4 kg / cnr overpressure for 10 minutes polymerized.

The temperature of the polymerization system was then raised to 60 ^° C. in the course of 20 minutes and propylene was fed in continuously and polymerization was carried out for 2.0 hours at 7 »0 kg / cm excess pressure.

For comparison purposes, the above polymerization was carried out in one stage for 25 hours at 60 ^° C., without the first polymerization stage at 40 ^° C.

The results are shown in Table V.

Table V

execution Polypro
pylen
powder
(6) Extraction
backlog in
boiling
n-heptane
(*> soluble
ches Po
lymeres
(ε) Schütt
density
(g / ccm) 2.7
2.5 the first
step 525
382 96.2
92.0 2 *. 3
16.7 0.38
* \ 0.32 there
(required acc.)
no
(Compare vers. '

Example 7 Preparation of the catalyst component A ^

10 g of the catalyst obtained by the preparation method for the catalyst of Example 1 was suspended in 150 milliliters of kerosene and, with stirring, was 3.4 millimoles

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ethyl aluminum, 13.6 millimoles of ethyl benzoate and 3.4 millimoles Titanium tetrachloride added successively at one hour intervals. After the implementation became the fixed portion of the product recovered by filtration, washed carefully with purified n-hexane and dried, using a catalyst component (A) obtained as atoms 2.2 percent by weight titanium, 60.0 percent by weight Chlorine and 10.8 percent by weight ethyl benzoate contained.

Polymerization

The polymerization of Example 6 was repeated, but 2.0 millimoles of triethylaluminum, 1.8 millimoles of ethyl benzoate and 0.20 millimoles calculated as titanium atom was added to the catalyst component (A).

For comparison purposes, the above polymerization was carried out in carried out the same way as in Example 6, but with the the first stage was omitted and the polymerization time was changed to 2.5 hours.

The results are given in Table VI.

Table VI

Execution Polypropy extraction (β) soluble Schütt 3.0 the first oil powder Residue 97.0 ches density 2.9 step in simmer 92.8 Poly the n-Hep meres tan (ε) (6) (g / ccm) there 537 27.7 O. Vk no 36 k 11.Ί 0.38

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Example 8 Preparation of Catalyst Component A

20 g of commercially available anhydrous magnesium chloride, 5> 3 g of n-butyl benzoate and 2.3 g of p-cresol were placed in a ball mill made of stainless steel (SUS 32) with an inner diameter of 100 mm and a capacity of 0.8 liters, the 2, Containing 8 kg of stainless steel balls (SUS 32) with a diameter of 15 mm, introduced under a nitrogen atmosphere and copulverized for 24 hours at an impact acceleration of 7 G. The resulting copulverized product (10 g) was suspended in 100 milliliters of titanium tetrachloride and, after the temperature of the suspension had been increased to 100 ^° C., was stirred for 2 hours. Then, the solid was recovered by hot filtration, washed with kerosene and hexane, and dried to obtain a titanium-containing solid catalyst component containing 2.8% by weight of titanium, 61.0% by weight of chlorine and 20.0% by weight of magnesium.

Polymerization

The inside diameter of a 2 liter autoclave was flushed with propylene and then charged with 750 ml of hexane, completely deoxygenated and moisture-free, 3.75 millimoles of triisobutylaluminum, 1.25 millimoles of ethyl p-toluate and 38 mg of the solid catalyst component prepared above . The mixture was stirred at 35 ° C. for 5 minutes and about 10 g of propylene were polymerized in the first stage. The polymerization system was then heated to 55 ° C. for about 5 minutes and a propylene gas with 6.2 mol percent ethylene was continuously fed in and polymerized for 2.0 hours at an excess pressure of 2.5 kg / cm. The results are shown in Table VII.

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Example 9 Preparation of a catalyst component (A)

A flask purged with nitrogen was charged with 50 ml of toluene and 12 ml of silicon tetrachloride, and 50 ml of a normal butyl ether solution containing 0.05 mol of n-butyl magnesium chloride was added dropwise to the mixture over 2 hours at 10 ° C the temperature of the mixture was raised to 60 ^° C. and it was stirred for 2 hours at this temperature. The solid material was recovered by filtration, washed fully with hexane and dried. The pulverized solid was suspended in 50 ml of kerosene and 1.1 g of ethyl * - o ^ tolyat and 0.8 g Äthylcyclohexancarboxylat were added Pas mixture was stirred for 2 hours at 80 ⁰ C. The supernatant was removed by decantation and was continued decanted using fresh solvent, was obtained until a complete washing 100th. Titantetraehlorid ml were added to 50 ml of a solids-containing suspension. the mixture was heated to 110 ⁰ C and subsequently. keyed 2 hours gerühr t. The supernatant liquid was removed by decantation and 100 ml of titanium tetrachloride was further added. The mixture was stirred for 2 hours at 130 ⁰ C and solid material was "recovered by filtration in VAER ^ me It was well washed with kerosene and hexane and dried to give a catalyst component (A) it * - hlelt, as atoms 1 , j? Containing weight percent titanium, 68.0 weight percent chlorine and 22.0 weight percent magnesium,

PolymerjL sat ion

gin propylene gas containing ethylene was among the same Polymerized conditions as in Example 8, but with tri'-n'-hexylaluminum instead of triisobutylaluminum, ^ .thyl-panisat instead of ethyl p-toluate and 67 mg of the solid catalyst component, prepared as above were used. The results are summarized in Table VII,

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Example 10 Preparation of a catalyst component CA)

A reactor was charged with 50 ml of a butyl ether solution containing 0.05 mol of n-butyl magnesium chloride in an atmosphere of nitrogen, and 0.5 mol of 2,6-dimethylphenol was added dropwise. The mixture was ^{heated to 70 °} C. and stirred for 2 hours. The butyl ether was removed by decantation and 5 ml of purified kerosene was added. In addition, 0.01 mol of ethyl p-anisate was added dropwise. The mixture was heated to 80 ° C. and stirred at this temperature for 2 hours. The solid portion was collected by filtration, washed with purified hexane and dried under reduced pressure. The resulting product was suspended in 100 ml of titanium tetrachloride and reacted at 100 ° C. for 2 hours with stirring. The supernatant liquid was removed by decantation and 100 ml of titanium tetrachloride was added. The mixture was ^{stirred at 100 °} C. for 2 hours and the solid fraction was obtained by filtering while warming. The solid portion was washed well with purified hexane and dried under reduced pressure to obtain a titanium-containing solid catalyst component containing 2.9% by weight of titanium, 59> O% by weight of chlorine and 19 »0% by weight of magnesium.

Polymerisation

A 2 liter autoclave was charged with 750 ml of deoxygenated and de-humidified hexane. While propylene gas, which contained 7.39 mole percent ethylene, was introduced, 3.75 millimoles of an organoaluminum compound with the average composition Et ₂ OAl (OEt) ₀ ^, 1.25 millimoles of methyl p-toluate and 37 milligrams of the solid catalyst component, as prepared above, charged. The autoclave was closed and 0.2 Nl Hg was introduced. The contents were stirred at 35 ° C. for 5 minutes to polymerize 12 g of the propylene gas. The analysis showed that the polymer formed in this way contains 2.1 mol percent ethylene in the first stage.

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held. The polymerization system was then ^{heated to 60 °} C. over the course of about 7 minutes. A propylene gas with 7139 mol percent ethylene was continuously charged and polymerized for 2.0 hours at a total overpressure of 2.5 kg / cm. The results are shown in Table VII.

Example 11 Preparation of the catalyst component (A)

Mg (0 <o » ₂ was made by reacting commercially available Mg (OCHj) ₂ with phenol. A stainless steel ball mill cylinder with a capacity of 0.8 liters and an inner diameter of 100 mm and with 2.8 kg stainless steel balls (SUS 32) having a diameter of 15 mm was charged with 0.2 mol of Mg (O ^ o) 2 and 0.033 mol of n-octyl benzoate in an atmosphere of nitrogen, and it was copulverized for 24 hours at an impact acceleration of 7G. The resulting solid product was suspended in 200 ml of titanium tetrachloride and the suspension was ^{stirred at 100 °} C. for 2 hours. The solid fraction was then recovered by hot filtration, washed well with hexane and dried to obtain a solid titanium-containing catalyst component which contained 2.8 percent by weight of titanium, 60.0 percent by weight of chlorine and 21.0 percent by weight of magnesium.

Polymerisation

A propylene gas containing ethylene was polymerized under the same conditions as in Example 10, except that 37 mg of the titanium-containing solid catalyst component prepared as above and 3> 75 millimoles of the organoaluminum compound having the average composition Etp qAIHq ^ were used . instead of the compound Eto qAl (OEt) Q y. were used and the amount of propylene gas polymerized in the first stage was 15 g. The results are shown in Table VII.

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36 Example 12

Polymerisation

3.75 millimoles of diethylaluminium chloride, 3.75 millimoles of n-butylmagnesium chloride prepared in kerosene, 1.25 millimoles of methyl p-toluate and 37 mg of the solid titanium-containing catalyst component prepared in Example 11 were charged into a 2 liter autoclave, in the order given under an atmosphere of propylene, the autoclave was closed, and 0.2 Nl of H ₂ was charged, and by stirring the contents for 5 minutes at 35 ° C., 9 g of propylene gas was polymerized in the first stage heated for 5 minutes to 60 ° 0. A propylene gas containing 6.58 mol percent ethylene was fed continuously and ^{polymerized at 60 ° C. for 2 hours at 2.5 kg / cm 2} overpressure The results are shown in Table VII .

Table VII

example powdery
total copoly
mere s (g) soluble
Polymer
(S) Bulk density
(g / ccm) Enamel
index 8th 98.7 7.9 0.29 14.6 9 96.4 7-9 0.30 24.5 IO 175.0 13.9 0.29 16.2 11 141.8 15.3 0.30 14.9 12th 128.9 9.6 0.30 5.5

ORIGINAL INSPECTED

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Claims (9)

Claims 1. A process for the preparation of α-olefin polymers or copolymers by polymerization or copolymerization of α-olefins having at least 3 carbon atoms at room temperature or a higher temperature under a pressure of about 1 to 100 kg / cm in the presence of a catalyst, comprising (A) a solid titanium complex catalyst component consisting essentially of magnesium, titanium, halogen and an electron donor and (B) an organometallic compound of a metal from groups I to III of the Periodic Table of the Elements, characterized in that the polymerization or copolymerization is carried out in two stages: (A) a first stage, wherein at least about 100 millimoles per millimole of titanium atom of an α-01efins are polymerized or copolymerized at a temperature of below about 50 ⁰ C to form a polymer or copolymer, the amount of which does not exceed about 30 percent by weight, based on the Endpi'odukt obtained in the second stage is and (b) a second stage, in which the end product is formed at a temperature above the temperature of the first stage and about 50 to about 90 ⁰ C. 2. The method according to claim 1, characterized in that that the polymerization or copolymerization continues in the presence an electron donor (C). 3. Process according to Claim 1, characterized in that a halogen / titanium Ncl ratio of component (A) of more than about 4 is used, and if component (A) is used with hexane 809810/0924 ORIGINAL A 27396ÜB is washed at room temperature, titanium is not substantially removed therefrom. 4 ·. Method according to claim 1, characterized in that that a magnesium / titanium molar ratio of at least about 5 is used. 5. The method according to claim 1, characterized in ", that an electron donor / titanium molar ratio of component (A) of from about 0.2 to about 6 is used. 6. The method according to claim 1, characterized in that that one uses an electron donor which is a member from the group of ketones with 3 to 15 carbon atoms, Aldehydes with 2 to 15 carbon atoms, organic acid esters with 2 to 18 carbon atoms, acid halides with 2 to 15 carbon atoms, ethers with 2 to 20 carbon atoms, Acid amides, amines and nitriles. 7. The method according to claim 2, characterized in that that the electron donation tox * (G) is an organic acid ester with 2 to 18 carbon atoms used. 8. The method according to claim 1, characterized in that there is used as component (B) an Orgcnoalumini-umverbindungen. 9. The method according to claim 1, characterized in that one works in the second stage at a temperature which is at least about 10 ⁰ C higher than the temperature of the first stage and about 60 to about 80 ⁰ C. 8 U U 8 1 0/0 9 2 4