DE2657917A1 - AGGLOMERATION-FREE CATALYST COMPONENT - Google Patents

Description

The invention relates to an agglomeration-free catalyst component of the type mentioned in the preamble of claim 1.

In particular, the invention relates to an at least substantially agglomeration-free finely divided titanium (III) chloride containing catalyst components, such as those used primarily for the polymerization of oc-olefins will.

It is known for the production of catalyst components based on titanium (III) chloride for the production of polymers from α-olefins titanium (III) chloride with an electron pair donator to move. This increases the stereo specificity and usually also the activity of the finished Catalyst comprising such a titanium (III) chloride electron donor catalyst component contains, improved (Keii,

709825/0949

TELEPHONE: (OB9) 85427O1! 8574O8O! (06O27) 8825 · TELEX: 621 777 Isard

"Kinetics of Ziegler-Natta Polymerization", Kodansha Ltd., Tokyo, 1972, pp. 163-173). Further examples of the use of such electron pair donor substances as auxiliary components in the grinding or ball milling of catalyst formulations, which are also titanium (III) chloride as a component are described in U.S. Patents 3,639,375 and 3,701,763. When grinding such electron pair donor substances together agglomerations frequently occur with titanium (III) chloride. Such agglomerated products are ind however, useless as catalyst components for the polymerization of α-olefins. The adverse effects an agglomeration on the catalytic properties of the catalyst components are known to the person skilled in the art.

To suppress agglomeration it is known from BE-PS 800 057 that when grinding is always below the agglomeration temperature to work. For the same purpose is known from DT-OS 23 42 200, the titanium (III) chloride in the presence of a metal hydroxide, sulfate, sulfite, -phosphate, phosphite, carbonate, cyanide, thiocyanate, nitrate and / or nitrite. Practical However, experience with these additives has shown that they have an unfavorable effect in such catalysts which are to be used in solvent-containing polymerization systems.

The invention is based on the object of creating a practically agglomeration-free catalyst component which is still free of agglomeration even in the finely divided state and, thanks to grinding, also over a wide temperature range can be easily produced.

To solve this problem, a catalyst component of the type mentioned is proposed, which according to the invention has the features mentioned in the characterizing part of claim 1.

709825/0949

»S.

The most important feature of the invention is that the catalyst component contains a substance during comminution or grinding to suppress agglomeration, which is hereinafter referred to for short as "agglomeration ^{suppressor 11.} This substance suppresses the aggregation tendency of the titanium (III) chloride catalyst component during grinding It ensures the formation of a fine powder with largely unaffected free ("discrete") particles, i.e. an agglomeration-free powder.

The term "agglomeration" is used in this context Description understood the random formation of aggregates or clusters of finely divided particles caused by the Crushing or grinding the titanium (III) chloride in the presence an electron pair donor substance is caused. This process or this phenomenon leads to a reduction the catalytic activity of the component.

It is known that small particles are polar in nature. In particular, finely divided titanium (III) chloride tends to form agglomerates, especially during grinding. The agglomeration tendency depends both on electrostatic repulsive forces or Coulomb forces between the individual particles and on the van der Waals ¹ see force acting between these particles. Corresponding experiments suggest that for a given particle size vertex and for a given particle environment the degree of agglomeration is a function of the combined potentials of the mutual interactions between the particles. The degree of agglomeration cannot be greater than the sum (V) of the electrostatic repulsion potentials (Ve) and the van der Waals' see attraction potentials (Va). For approximately spherical particles, the mathematical expressions for the potentials Ve and Va are given by the equations (I) and (II) (see below). Since the van der Waals see attractions

70982 5/0949

forces are pronounced close-range forces predominate the forces of attraction versus the electrostatic repulsive forces when the particle size of a particle is reduced Systems. This leads to the fact that by their nature, polar particles are finely divided in the case of intense and long lasting grinding tend to agglomeration more strongly and more rapidly than larger particles. This agglomeration in a mixture of titanium (III) chloride and an electron donor substance suppressing and independence when marrying together and after marrying together The object achieved by the invention is to keep the individual finely divided particles of the powder "discrete". The invention solves this problem by adding a Agglomeration suppressor.

The following classes of compounds serve as agglomeration suppressors for the purposes of this description:

(a) Compounds which, by adsorption on the finely divided particles, cause the interaction forces between these particles can influence and thus keep them independent of each other. To this class of compounds calculate in particular ionic compounds. It can be assumed that the effectiveness of these substances depends on it is based on the fact that it has the surface potential (zeta potential) of particles increase.

(b) Sufficiently large polarizable substances that the contact between the individual particles of the catalyst component sterically hinder. Such steric hindrance causes the agglomeration of the catalyst particles also suppressed.

In summary, it can be said that the agglomeration suppressor is a substance which either modifies the interaction forces existing between the catalyst particles or which becomes steric between these particles

709825/0949

• V.

Obstacles or barriers leads to a direct mutual contact of the individual particles among themselves prevented.

For a better understanding of the invention, the following first refers to the titanium (III) chloride and the electron pair donor substances received, which marry together in the presence of the selected agglomeration suppressor will.

The titanium (III) chloride used for the catalyst component of the invention can be prepared in a wide variety of ways are, preferably by one of the following processes: (a) Reduction of titanium (IV) chloride with a Metal such as aluminum or titanium, with the reduction product either crushed or not crushed can be used, (b) reduction of titanium (IV) chloride with hydrogen, (c) reduction of titanium (IV) chloride with an organometallic compound such as aluminum alkyl. (d) Joint grinding of titanium (III) chloride with a halide of a metal of the third group of the periodic table of the elements, for example with a Aluminum halide.

Examples of particularly suitable starting substances for the titanium (III) chloride component are available to those skilled in the art known from numerous publications. In this regard, see particularly U.S. Patents 3,639,375 and 3,701,763 referenced, in which titanium (III) chlorides are described as starting substances for the catalyst component of the invention are particularly suitable.

The starting material obtained in this way or by another process is then shared with an electron pair donor substance and the agglomeration suppressor

709825/0949

Grind to the end product, the agglomeration-free catalyst component.

Substances such as those mentioned in US Pat. Nos. 3,639,375 and 3,701,763 are preferably used as electron pair donors. Such electron pair donors improve the stereo specificity or both the stereospecificity and at the same time the activity of the catalyst component or the Catalyst. For the catalyst component of the invention, the electron pair donor can be selected from the following classes of compounds to be selected:

Organic oxygen-containing compounds such as aliphatic ethers, aromatic ethers, aliphatic carboxylic acid esters, cyclic carboxylic acid esters, aromatic carboxylic acid esters, unsaturated carboxylic acid esters, aliphatic Alcohols, phenols, aliphatic carboxylic acids, aromatic carboxylic acids, aliphatic carboxylic acid halides, lactones, aromatic carboxylic acid halides, aliphatic ketones and aromatic ketones;

organic nitrogen-containing compounds, such as, for example, aliphatic amines, aromatic amines, heterocyclic ones Amines, aliphatic nitriles, aliphatic carbamates, aromatic nitriles, aromatic isocyanates and aromatic Azo compounds;

Oxygen and nitrogen containing compounds such as aliphatic and aromatic amides and Guanidines and their alkyl-substituted derivatives;

organic phosphorus-containing compounds such as aliphatic phosphines, aromatic phosphines, aliphatic Phosphites and aromatic phosphites;

Compounds containing phosphorus and nitrogen, such as

709825/0949

for example phosphoric acid amides;

Compounds containing phosphorus and oxygen such as triphenylphosphine oxide;

Sulfur-containing compounds such as carbon disulfide, aliphatic thioethers and aromatic Thioether; and

organic silicon-containing compounds, both monomers, such as tetrahydrocarbylsilanes, organohydrogenosilanes, Organohalosilanes, organoaminosilanes, organoalkoxysilanes, organoaryloxysilanes, organosilicon isocyanates and organosilanol carboxylic acid esters as well as polymers such as polysilalkylenes, Organopolysilanes, organopolysiloxanes, oc, u> -dihalogenoorganopolysiloxanes, Organocyclopolysiloxanes and polysilazanes.

The dipole moment of the electron pair donors is preferably in the range of 0.5 to 6.0 Debye units.

The following electron pair donors are particularly suitable for the catalyst component of the invention used: hexamethylphosphoric acid triamide, dimethylformamide, benzonitrile, γ-butyrolactone, dimethylacetamide, N-methylpyrrolidone, triphenylphosphine oxide, N, N-dimethyltrimethyl acetic acid amide, Toluene diisocyanate, dimethylthioformamide, ethylene carbonate, trilauryl trithiophosphite, tetramethylguanidine and methyl carbamate.

Other electron pair donors are known to those skilled in the art. Examples of such substances can be found in the üS-PSen 3 639 375 and 3 701 763, to which reference is made.

The third essential component for the catalyst together: The invention is based on the agglomeration suppressor.

709 825/0949

.01.

The task of the agglomeration suppressor is to prevent agglomeration when grinding the titanium (III) chloride with the electron pair donor to prevent. The two classes of agglomeration suppressors are mentioned above.

The first class of agglomeration suppressors includes those ionic compounds that are adsorbed on the finely divided Particles can change the zeta potential of these particles, so as to prevent the particles from agglomerating. The following ionic compounds are preferably used:

(1) Ionic salts of the metals of the first main group (group Ia) of the periodic table of the elements. This is within the framework of this description, the binding reference system in "Handbook of Chemistry and Physics", 57th edition, CRC Press, Cleveland, Ohio, pp. B-4, reprinted Periodic Table of the Elements. Examples of this group are salt-like halides, such as lithium fluoride, lithium chloride, lithium bromide and lithium iodide and the analogous halides of the elements sodium, potassium, rubidium and cesium. The alkali metal salts of other more common anions such as Sulphates, nitrates, stearates, borates, silicates, aluminates, citrates and thiosulphates are in this class of substances also particularly suitable compounds. The alkali metal salts also belong to this class of substances the benzenesulfonic acid and the alkylsulfonic acids with 1 to 20 carbon atoms in the alkyl. Most of all it has grown out of this Sodium benzene sulfonate class of substances proven to be the compound with the best results.

(2) Ion salts of the metals of the second main group (group Ha) of the periodic table of the elements, which correspond to the above correspond to the salts mentioned under item 1.

(3) ion salts of transition metals. In this group are Preferably copper stearate because of its excellent results and

(4) Quaternary ammonium salts of the general chemical formula R ₄ NX ~, in which R is hydrogen, alkyl or aryl and X is halogen or sulfate. From this group, preference is given to using the trialkyl hydrochlorides, the trialkyl hydrobromides and the trialkyl hydroiodides, the trialkyl moiety particularly preferably having 1 to 4 carbon atoms. The best results are achieved with the preferred triethylamine hydrochloride.

(5) Substances that are grouped under the heading of ionic surface-active substances. One a detailed description of the substances in this class can be found in the "Encyclopedia of Surface Active" Agents ", J.P. Sisley, Chemical Publishing Co., New York, Volumes I and II, 1961 and 1964.

(6) The finely divided water-soluble ammonium salt of an amidopolyphosphate, in which practically all the particles have a grain size of less than 5 μm. The salt is obtained by reacting P ₂ 0 _g in the dry vapor phase with anhydrous ammonia (US Pat. No. 2,122,122). The salt produced in this way shows the following typical analysis:

^P 2 ° 5
NH ₃ (free) 76.1
15.4 NH ₃ (total) 22.4 Amide nitrogen as
NH ₃ 7th pH (1% solution) 5.6

Ammonium amidopolyphosphates of this type are commercially available ("Victamide", Stauffer Chemical Co.). Substances of this kind are used as one component of a four-component mixture, the coarse-grained sodium chloride as an anti-caking agent

709825/0949

and antifreeze is added (U.S. Patent 3,428,571). These
However, use does not suggest the use of such ammonium amido polyphosphates as agglomeration suppressors in the production of titanium (III) chloride catalysts.

When using water-insoluble ammonium polyphosphates, inactive catalyst components are obtained.

(7) Salts of aliphatic tricarboxylic acids, in particular of alkane tricarboxylic acids having 1 to 4 carbon atoms and hydroxyl-substituted derivatives of the above two groups of acids. From this group, the preferred acid is 2-hydroxy-1,2,3-propane tricarboxylic acid (citric acid) used. Surprisingly good results are obtained in this group of salts with salt mixtures of alkali metal salts and alkaline earth metal salts on the one hand and transition metal salts on the other hand. Under this type of mixture a mixture of calcium citrate and iron (III) is preferred ammonium citrate is used. The use of dicarboxylic acid salts, such as tartrates, is surprisingly ineffective.

(8) Alkyl alkali metal sulfates preferably 6 to 18 Carbon atoms in the alkyl radical. Dodecyl sodium sulfate is preferably used as being particularly suitable.

(9) alkaline earth metal phosphates. The tribasic calcium phosphate is preferably used.

(10) alkaline earth metal titanates, preferably calcium titanate.

(11) Non-gaseous halogens, such as iodine, the has a covalent bond character in the free state, with Titanium (III) chloride, however, forms an ionic body in situ.

709825/0949

The second group of agglomeration suppressors are polarizable Compounds adsorbed by the particles of the catalyst component. The adsorbed polarization suppressors create steric hindrance and thereby prevent direct contact between the individual titanium (III) chloride particles of the catalyst. The agglomeration suppressor molecules of this type have either a chain length and / or a diameter in its longitudinal conformation in the range from 1 to 20 nm.

Tests have shown that an agglomeration of titanium (III) chloride particles can obviously be suppressed if the following inequality is satisfied:

I ₃ + I ₄ > k

In this inequality, I ₃ denotes the threshold distance created in the system by the electron pair donator, 1. the threshold distance created in the system by the agglomeration suppressor, and k is a constant that can be determined by setting the first derivative of the mathematical expression for the total potential (V) of the system to zero.

The mathematical expression for the total potential of the system is the sum of the additive effects of the electrical repulsion potential (Ve) and the attraction potential (Va). These partial potentials can be passed through reproduce the expressions I and II:

Ve = (Epsilon · a ² «zeta ² ) / R (I)

In this equation, epsilons mean the dielectric constant of the medium, R the distance between two neighboring ones Particles, a is the mean radius of the particles in the medium and zeta is the zeta potential, which is the surface potential of the spherical particle.

709825/0949

-A

Va = - ^

2. , _ / S ² -4

⁶ S * -4

+ - + In

(ID

In Equation II, A is Hamaker's constant and S = R / a, where R and a are as defined above. the Calculation of the Hamaker constant is described in Hamaker, H.C, Physica 4 (1937), 1058.

The functions explained above show that the physical properties of the electron pair donor, so in particular its grain size, its dipole moment and its dielectric characteristics have a significant influence on the Have choice of agglomeration suppressor.

Polar agglomeration suppressors are preferably used below for the catalyst component of the invention described in more detail:

(1) Compounds of the general chemical formula

A ^ .A

^ P (O) OP (O)

In this formula, A is one of the radicals OR, NRR 'or OH, where R and R ^{1 are} each an alkyl radical having 1 to 4 carbon atoms and at least one of the radicals A is either OR or NRR ¹ .

From this class of substances, preference is given to using the alkyl pyrophosphoric acid amides, in particular octamethyl pyrophosphoric acid amide. In this compound, based on the above-mentioned general chemical formula, all radicals A have the meaning NRR ¹ , all groups R and R ^{1 being} methyl groups. These compounds are known from GB-PS 1,372,920 as catalyst components for olefin polymerization, but according to the prior art they are used in significantly larger amounts and in higher concentrations.

709825/0949

centrations used as in the context of the invention. The use of these compounds is from the cited publication as an agglomeration suppressor neither known nor suggested by them.

Another group of substances that fall under the general chemical formula mentioned above and are preferred are used for the catalyst component of the invention, the alkyl pyrophosphates, in particular the acidic alkyl pyrophosphates, in which, based on the aforementioned general chemical formula, the radicals A have the meaning OR and OH, and where at least one of the radicals A has the meaning OR. From this group are preferred in particular the acidic dialkyl pyrophosphates with 1 to 4 carbon atoms, in particular the acidic dimethyl pyrophosphate is used.

If all A radicals in the above-mentioned general chemical formula have the meaning OH, this would be Correspond to pyrophosphoric acid. A marriage of the starting substances with pyrophosphoric acid, however, leads to a catalyst component whose activity is due to agglomeration is noticeably degraded.

(2) Trialkyl phosphates of the general chemical formula

(RO) ₃ PO

where R is an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms. From this group becomes particular tributyl phosphate is preferably used. US Pat. No. 2,956,991 discloses the use of such compounds as the third component in titanium (III) chloride catalysts is known in significantly larger quantities, but is this publication does not suggest the use of such trialkyl phosphates in significantly lower concentrations

709825/0949

- 14 -

to be used as an agglomeration suppressor.

(3) Polymeric silicon compounds, namely amorphous silicon dioxide and siloxanes.

So-called amorphous silicon dioxide is an essentially dehydrated polymeric silicon dioxide, which is known as polymeric Condensation products of orthosilicic acid can be understood. Amorphous silicon dioxide is preferably used in the frame of the invention uses colloidal silica. Such colloidal silica is commercially available ("Cab-O-Sil"; Cabot Corporation). This material is made up of colloidal silica particles that form in chain-like formations are sintered together. In their longitudinal extension, these particles are typically for such finely divided Silicon dioxide has an average grain size in the range of about

-3 -3
7 * 10 to 14 · 10 μπι and a specific surface area in

Range from about 175 to 420 m ² / g. It is known to use silicon dioxide powder as an anti-caking agent for a wide variety of applications (US Pat. No. 2,728,732), but none of these applications suggest the use of the silicon dioxide described above as agglomeration suppressors for the catalyst components in question.

Further particularly effective agglomeration suppressors for the special purpose considered in the context of this description are the siloxanes. Such siloxanes are unbranched chain compounds that correspond to the alkalis in carbon chemistry. The siloxanes that can be used in the context of this invention are made up of molecular chains that are composed of oxygen atoms bonded silicon atoms are made up and are arranged so that each silicon atom with two oxygen atoms connected is. Preference is given to using alkyl-substituted siloxanes whose alkyl radicals are in particular 1 to 4 carbon contains atoms. Hexamethylsiloxane and polydimethylsiloxane in particular are preferably selected from this class of substances

709825/0949

used. In particular, the hexamethylsiloxane is an example of a compound that is used in the context of the invention as an agglomeration suppressor can be used and has a chain length of less than 1.0 nm.

When using a non-polymeric silicon compound such as for example ethyl silicate, becomes merely a catalyst component with noticeably reduced activity.

(4) Dialkyl phosphoric acids of the general chemical formula

Il

(RO) ₂ POH

in which R is an alkyl radical, preferably an alkyl radical having 1 to 6 carbon atoms in the alkyl group. As special A suitable compound from this class of substances is preferably diisoamylphosphoric acid, which means that the Alkyl group is the isoamyl radical.

(5) Dialkyl maleate and dialkyl fumarate, preferably with 1 to 4 carbon atoms in the alkyl radicals. From this class of substances, diethyl maleate is preferably used.

(6) The reaction product of a compound of the formula (CgH ₅ ) ₂ Si (OH) ₂ iat a titanate of the formula Ti (OR) .. Here, R is an alkyl group with preferably 1 to 4 carbon atoms. The preparation of this reaction product is known from US Pat. No. 3,758,535.

(7) Compounds of the formula RCONH ₂ , in which R is an alkyl group with preferably 1 to 18 carbon atoms , and the polymeric alkylamides. Propionic acid amide, stearic acid amide and polyacrylamide are the three most important representatives of agglomeration suppressors of this class, which also includes compounds with a chain length of less than 1 nm.

709825/0949

(8) Solid elements, namely graphite, amorphous carbon and sulfur. From this group are preferably graphite, one of the two allotropic crystalline modifications of carbon (the other is diamond) and sulfur are used.

(9) strength.

(10) Alkyl ketones with 20 to 30 carbon atoms in total, i.e. with 20 to 30 carbon atoms if the carbon atoms of both alkyl groups of the ketone are added together. Preferably laurones of the formula (C ₁₁ H ₂₃ J ₂ C ^{0 and} the

14-heptacosanone of the formula (0, .3H ₂ -) ₂ CO ^used

(11) Epoxides and their polymeric derivatives, but not monomeric ethylene oxide and propylene oxide. Preferably be from this class of substances the diepoxide of cyclohexenylmethylcyclohexenecarboxylate and the polyethylene oxide which is a water-soluble polymer obtained by polymerizing of ethylene oxide is obtained, for example, in the presence of an alkaline catalyst.

(12) Trialkyl borates with preferably 1 to 4 carbon atoms in the alkyl radical. Some of these connections point Chain lengths of less than 1 nm. From this group, preference is given to using trimethyl borate. The use boric acid itself cannot prevent agglomeration.

(13) Urea and alkyl substituted ureas, preferably having 1 to 4 carbon atoms in the alkyl group. Even these substances include compounds with a chain length of less than 1 nm. This group preferably includes Urea itself and tetramethylurea are used.

(14) Alkylenedxamine tetraacetic acids preferably having 2 to 4 carbon atoms in the alkylene group. From this group

709825/0949

. 33.

Ethylenediaminetetraacetic acid is preferably used. The alkali metal salts of these acids are ineffective.

(15) Water-soluble cellulose ethers, especially methyl cellulose and sodium carboxymethyl cellulose.

(16) _r especially phthalocyanine phthalocyanine, copper phthalocyanine, chlorinated copper phthalocyanine and sulfonated copper phthalocyanine. In particular, copper phthalocyanine is preferably used.

(17) Acrylates with 1 to 4 carbon atoms, which also contain compounds with chain lengths of less than 1 nm. Methyl acrylate is preferably used.

(18) Compounds of the general chemical formula (PNX ₂ ), where X is chlorine or bromine and η 2, 3 or 4.

From this group, preference is given to using compounds of the formula), where η is 3 or 4.

(19) Connections with the formulas

a) (C ₆ H ₁₁ J

b) ((C ₆ H ₁₁₃₂

in which R is an alkyl radical having 1 to 6 carbon atoms.

Process for the preparation of the compounds a) are from BE-PS 783 532 and for the preparation of the compound b) from the U.S. Patent 3,264,177 is known.

(20) Non-gaseous α-olefins, preferably 1-eicosene.

709825/0949

It is important to point out that not all possible polarizable compounds are selected with each individual case Electron pair donors act as effective agglomeration suppressors. For example, 2-undecanone is available as Agglomeration suppressor ineffective when hexamethylphosphoric triamide is used as an electron pair donator. This proves the facts set out above that the Effectiveness of the agglomeration suppressor selected in each case for the catalyst component on the choice of used electron pair donor depends.

For the previously known areas of use, the three constituents of the catalyst component of the invention are preferred used in certain proportions.

The electron pair donor is preferably used in an amount of 2 to 15% by weight, based on the titanium (III) chloride, preferably in an amount of 2.5 to 10% by weight. In general, it can be assumed that the electron pair donor should be present in at least an amount which is at least sufficient to form a monomolecular layer on the titanium (III) chloride particles. The amount of electron pair donor preferably used thus depends on the molecular weight of the electron pair donor and the effective surface area of the titanium (III) chloride. The use of too large an amount of electron pair donor poisons the catalyst component, while the use of too small an amount of electron pair donor does not bring about the desired degree of improvement. The person skilled in the art can determine the amount of electron pair donor required in each case in a manner known to him without inventive intervention. As a guideline for achieving good results, it can be assumed that approx. 6% by weight of hexamethylphosphoric acid triamide (HMPT) are required. This electron pair donator has the chemical formula [(CH ₃ J ₂ N] ₃ PO. For the approximate determination of the amount of any

709825/0949

other selected electron pair donator ("Compound X") of a molecular size comparable to that of HMPT, the following equation can be used:

Link X (%) = ^ A * MG.

^MG HMPT connection X

where MG is the molecular weight. Molecules with a smaller adsorption cross-section than HMPT require for Achieving equally effective monomolecular adsorption layers correspondingly larger amounts, while larger Molecules require correspondingly smaller amounts of substance.

The agglomeration suppressor is only required in small quantities to achieve the desired effect. To effectively suppress agglomeration, in general, based on the weight of the electron pair donor s, only 0.1 to 5 wt .-% agglomeration suppressor used. Preferably, based on weight of the electron pair donor, 0.6 to 3.0 wt% agglomeration suppressor used. In detail, the amount of agglomeration suppressor required depends on the species and amount of the electron pair donor used and the mean grain size of the titanium (III) chloride. It is known that the mean grain size of the titanium (III) chloride depends in particular on the grinding time, the grinding speed and the configuration of the grinding device away. Particles obtained by rapid comminution (high comminution speed) tend to be stronger and faster to agglomerate than larger particles obtained by slower crushing. For smaller grain size distributions, larger amounts of agglomeration suppressors are required. The shredding speed R for the purposes of this description is given in the definition of Berry et al., Proc. Intern. Cong. Surfact

709825/0949

Activity, London, (1957) pp. 196-202. In this sense, the shredding speed is a function the surface S of the ground material and the grinding time t: R = S / t.

The comminution or grinding within the scope of the invention is preferably made by marrying the two together mentioned starting materials with the agglomeration suppressor also described in more detail above under common ones Temperature and time conditions carried out. So can the grinding in a ball mill or another Grinding device in the absence of diluents in an inert atmosphere, such as nitrogen or argon, which are practically free from oxygen, water and other catalyst poisons, at a temperature above take place for a period of time that is sufficient to comminute the feed mixture to a powdery mixture, which at Combination with organoaluminum compounds results in a catalyst that has good activity and good Stereospecificity in the polymerization of α-olefins having.

When using a rotating ball mill is preferably about 30 to 90 ground at a temperature in the range of 30 to 70 ⁰ C. In certain systems, however, shorter grinding times are also sufficient. Particularly good results are achieved when the temperature in the range between 45 and 70 ⁰ C, is preferably maintained in the range between 50 and 60 ⁰ C, and the grinding time to 80 h about 40 microns. A particularly suitable comminuting device is known from US Pat. No. 3,688,992. With this device, which enables high grinding speeds, meals between 3 and 12 hours can be expected. However, this does not mean that longer meals cannot be maintained.

709825/0949

The temperature is measured directly and currently inside the ball mill. Temperatures exceeding 70 ^° C. should be avoided, since above this temperature agglomeration of the catalyst component and thus deactivation of the finished catalyst usually cannot be avoided even if the agglomeration suppressor of the invention is added to the mixture to be ground.

As already described above and as is clear from the examples, numerous factors go into the selection and the quantity selection of the agglomeration suppressor. The type of each plays an important role selected electron pair donator. Auah plays a role for which operating conditions and under which circumstances the agglomeration suppressor is needed. For example, 1-Eicosen and Triton X-100 are extremely unfavorable when they are ground with dimethylacetamide, while the best results are obtained with the ionic agglomeration suppressor sodium chloride. The test results also show that too large amounts of either the electron pair donor or the Agglomeration suppressor or both substances, instead of suppressing the agglomeration, induce or intensify it. Even if a certain minimum concentration of the electron donor is used to achieve the desired properties is absolutely necessary, however, too much can mean that the intended polymer is not is obtained.

In addition, the grinding conditions, such as the temperature and the number of balls in a ball mill in the agglomeration probability. So leads for example an increase in the number of balls in the mill when using γ-butyrolactone in the absence

709825/0949

an agglomeration suppressor to initiate agglomeration, while with benzophenone the same effect is obtained by increasing the grinding temperature. These data show that an agglomeration suppressor is added in the commercial production of the catalyst components
should be added in order to prevent agglomeration of the ground starting substances in the event of unforeseen changes in the grinding parameters, even then,
if the laboratory tests carried out initially have a
Agglomeration could have switched off.

The product of the invention is made by grinding together titanium (III) chloride, the electron donor and the
Agglomeration suppressor manufactured and then can be used in
Connection with common organoaluminum compounds
be used for the polymerization of α-olefins. This polymerization can be carried out under conventional conditions.

Suitable organoaluminum compounds are the substances known and used per se, in particular aluminum alkyls, preferably the following: trimethyl aluminum, triethyl aluminum, tributyl aluminum, triisobutyl aluminum, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, diethyl aluminum aluminum chloride, ethyl aluminum aluminum chloride, diethyl aluminum chloride and diethyl aluminum chloride. The ethylaluminum compounds, especially triethylaluminum and diethylaluminum chloride, are preferred as organoaluminum compounds
used.

The catalyst component of the invention can be used for the production of polymers as α-01efinen with in particular 2 to 8 carbon atoms, also for propylene homopolymers, propylene copolymers, ethylene copolymers and ethylene homopolymers as well

709825/0949

26b7917 -Si

for polymers of 1-butene _r 3-methylbut-1-ene and 4-methylpent-1-ene are used. The polymerization of these monomers is usually carried out at a temperature somewhere in the range between about 10 and 150 ° C. under pressures in the range from 1.5 to 100 bar.

The invention is explained in more detail below on the basis of exemplary embodiments.

example 1

3.2 g of pure hexamethylphosphoric triamide are weighed in with 0.032 g of one of the agglomeration suppressors mentioned in Table I in Example 4. The mixture is filled into a stainless steel ball mill with a clear diameter of 11 cm and a length of 15 cm in a glove box under nitrogen and with the exclusion of air and moisture. The mill is charged with 875 g of stainless steel grinding balls which are 1 cm in diameter and which are magnetized. The mill is shaken until a film of liquid has formed around the grinding balls and on the inner walls of the mill. Titanium (III) chloride obtained by reducing titanium (IV) chloride with metallic aluminum is then added. The added product is a cocrystallized product of the formula 3TiCl ₃ -AlCl ₃ , which is commercially available ( ¹¹ TiCl ₃ A ", Stauffer Chemical Co.). After filling, the mill is then hermetically sealed and rotated for 110 min "Rotated at 50 ^° C. for 48 h. The temperature is controlled by a thermocouple that is inserted in an oil bath in the ball mill. The measured temperature is fed to a controller and a recording device. If necessary, the mill is heated by an infrared heater. After 48 h, the practically completely agglomeration-free catalyst component is transferred to a closable vessel in a dry box and then

709825/0949

checked. The test with regard to the activity and the isotactic index are described in more detail in Example 2.

Unless expressly stated otherwise in the following examples, the method and parameters of the example described above are used. _{3TiCl 3} -AlCl _{3 is} used in all examples. Except for Example 14, the agglomeration is observed optically. If the percentage agglomeration is not mentioned in the table below, this means that at least 30% of the total substance is agglomerated.

Example 2

The catalyst components prepared according to Example 1 are in terms of their activity and isotactic Polymerization product index checked:

A 4! Autoclave equipped with a stirrer and jacket thermostat is charged with 1 liter of dry heptane. The stirring speed is 600 min ". 0.3 g of the catalyst component obtained according to Example 1 is suspended in heptane under a nitrogen atmosphere. 8 ml of a 20% strength by weight solution of diethylaluminum chloride in heptane are then added. Another liter of dry heptane is added the autoclave is closed, the temperature is increased to 70 ^° C., the autoclave is rinsed, ^{pressurized with hydrogen (0.22 bar / cm 2} ) and charged with propylene under a constant pressure of 9.8 bar / cm ^a Purified on a column charged with a copper catalyst to remove even the last traces of oxygen, and is then passed through a molecular sieve (Linde 4A) to remove the last traces of water. The test polymerization is carried out for 4 hours -Water mixture decomposes. The polymer is removed by filtration

709825/0949

separated and ^{dried at 70 0} C overnight and then weighed.

About 6 g of the dry polymer are extracted with heptane in a Soxhlet apparatus for 3 hours. The percentage of the unextracted part of the polymer is referred to below as "C7i ^H. A measured portion of the filtrate is evaporated, the residue is weighed out and the total proportion of the soluble or atactic polymer is determined from this.

The activity is defined as the amount of dry solid polymer in grams that is obtained per gram of the TiCl ₃ -containing catalyst formulation prepared according to Example 1.

The isotactic index (II) is defined as follows:

ti - C7i »Weight of solid polymer total weight of the ore Polymers

The total weight of the polymer obtained in the test polymerization is composed of the insoluble polymer described above (isotactic) and the soluble (atactic) polymer component together.

Example 3 (comparative example)

A titanium (III) chloride catalyst component modified with an electron pair donor is absent an agglomeration suppressor manufactured as follows:

3.2 g of pure hexamethylphosphoric acid triamide (HMPT) are weighed into a small glass vessel and placed in the ball mill also used in Example 1. Then 50 g of TiCl ₁ A are placed in the ball mill. The mixture is after

-1 Close the mill with a speed of rotation of 110 min and grind at 50 ^° C. for 48 h. After the end of the grinding period, the mill is opened under an inert gas atmosphere. The TiCl ₃ / HMPT

709825/0949

Mixture is obtained lumpy and shows a tendency to to adhere to the walls of the ball mill and to the grinding balls. The millbase obtained could not be used for propylene polymerization can be used.

Example 4

The following Table I shows the activities and the isotactic index values for numerous according to Example 1 produced catalyst components, which were tested according to Example 2 and an agglomeration suppressor contain. Substances for which the data columns only show stars are used as agglomeration suppressors ineffective and serve as comparison substances to the respectively immediately preceding, these structurally similar substances.

Table I ++)

Tested agglomeration suppressor

Activity Isotactic Index

Octamethylpyrophosphoric acid amide

acid dimethyl pyrophosphate pyrophosphoric acid tributyl phosphate ammonium amidopolyphosphate (water soluble) 1 ammonium amido polyphosphate (water insoluble) ² amorphous silicon dioxide hexamethylsiloxane polydimethylsiloxane diisoamy! phosphoric acid diethyl maleate

1450 94.5 788 95.8 1369 95.1 1357 94.8 1440 93.6 996 94.9 1362 94.7 1369 94.4

709825/0949

4th
in u \ c-5 foul + τη / nnttΓρη Ii ιαλω Q4

6 5 2 I i / L η

Triethylamine hydrochloride 1482

Propionamide 1431

Stearic acid amide 1314

Polyacrylamide 1341

Graphite 1460

Sulfur 1477

Iodine 1324

Sodium chloride 1413

Sodium Benzene Sulphonate 1360

Lauron, 1507

Diepoxide of Cyclohexenylmethylcyclohexenecarboxylate - * 1128

Polyethylene oxide 1323

Calcium borate 1093

Trimethyl borate 1162

Boric acid +)

Urea ^: 944

Tetramethylurea 858

Zinc stearate 1293

Copper stearate 1455

Magnesium stearate +) +)

Ethylenediaminetetraacetic acid 1454 92.1 Sodiumethylenediaminetetraacetate +) +)

Calcium citrate

Iron (III) ammonium citrate calcium tartrate

Dodecy! Sodium sulfate methyl cellulose

Sodium carboxymethyl cellulose copper phthalocyanine starch

Sodium thiosulfate

Methyl acrylate

tribasic calcium phosphate calcium titanate

709825/0949

93 , 2 93 , B 94 ,1 93 ,8th 92 ,1 93 , 2 93 ,1 94 , 3 93 , 7 94 , 5 94 , 5 93 , 5 95 , 0 93
» /1
\ T
92 I.
, 2 92 , 3 91 ,1 94

1346 89.0 1492 93.7 1310 94.7 1066 95.5 1386 881 93.2 1056 95.9 949 95.3 1461 92.0 1104 95.5 1275 94.9

- ytr- 1393 2657917 * . η. 1372 94.7 1039 88.4 87.9

(PNCl ₂ ) ₃ or (PNCl ₂ ) ₄
(C ₆ H ₁₁ J ₃ SnSP (S) (OiPr) ₂
[(C ₆ H _1. ,) 3Sn] ₂ S

Footnotes:

1) Commercially available ("Victamide", Stauffer Chemical Co.)

2) Commercially available ("Phöschek P-30", Monsanto Co.)

3) Commercially available ("Cab-O-Sil", grade M-5, Cabot Corporation)

4) Manufactured in accordance with U.S. Patent 3,758,535

5) Commercially available ("ERL-4221", Union Carbide Co.)

6) Manufactured according to BE-PS 783 532 or US-PS 3,264,177

++) The agglomeration tendency is a function of the grain size, which in turn is determined by the grinding parameters. Under milling conditions different from those given in the data Table I, the activity and isotactic index values may differ when used equal amounts of agglomeration suppressor can be obtained.

Example 5

In this example, the increase in activity and the isotactic index are shown, which can be obtained when the grinding temperature range, which is preferably to be maintained according to the development of the invention, is maintained. This preferred range of the milling temperature of about 50 ⁰ C is compared with grinding results obtained at room temperature, both in the presence and in the absence of 6 to 8 wt .-% HMPT in the catalyst component, based on the weight of the 3TiCl ₃ -AlCl ₃ . The catalyst component is that described in Example 1

709825/0949

Way prepared and then in the manner described in Example 2 for the determination of the activity and the isotactic Index checked. Meals of 48 and 72 hours are set as shown in Table II. The results are summarized in Table II.

709825/0949

CD
CD
OO

Table II

Catalyst component milling in activity I.I. Activity I.I.

Ball mill (h) (50 ⁰ C) 50 ⁰ C (room temp.) * (Room temp.)

3TiCl ₃ 'AlCl ₃ , It8 1? J8 66.2 61 $ 62.6

3TiCl ₃ * AlCl ₃ 72 1402. 68.7 I070 88.2

5TiCl ₃ -AlCl ₃ +

6-8 # HMPT ** kQ 11 »09 93.6 881 Qy.

3TiCl ₃ -AlCl ₃ +

6-8 # HMPT ** 72 U50 94.Ο Ι267 88.5

* ■), the actual temperature inside the ball mill for about 35 ⁰ C. * t *) The HMPT contains 0.2 wt .-% Octamethylpyrophosphorsäureamid as agglomeration suppressors.

After the method described in Examples 1 and 2, numerous electron pair donors (ED) and one Range of agglomeration suppressors (AC) tested. The results obtained are summarized in Table III,

709825/0949

Table III

ο co -ρω

ED Wt% Dimethylformamide 2.2 Dimethylformamide 2.5 Dimethylformamide 4.1 Benzonitrile 3.0 Benzonitrile 3.1 γ-butyrolactone 5.8 γ-butyrolactone 6.2 n-butyl laurate 6.2 Dimethylacetamide 3.0 Dimethylacetamide 2.9 Dimethylacetamide 4.0 Dimethylacetamide 3.0 N-methylpyrrolidone 3.5 N-methylpyrrolidone 3.5 N-methylpyrrolidone 4.6 Triphenylphosphine oxide 9.0

AC

% By weight ++) activity

N, N-dimethyltrimethyl-acetic acid amide 4.4

N, N-dimethyl trimethyl less igsäureamid 4.5

14-heptacosanone 3.6

Sodium chloride 3.0

14-heptacosanone 1.8

14-heptacosanone 2.6

Lauron 1.5

Sodium chloride 1.1

Strength 1.1

Thickness 0.8

Iodine 2.0

Sodium chloride 2.2

Sodium Chloride 2.1 Triton X-100 ++ - H-) 2.0

Iodine 1.7

1-eicosen 2.0

Iodine 1.9

Sodium bromide 2.3 sodium bromide 2.1

1-eicoses

+++)

1302

1323

+++)

+++)

1353

1467

1167

+++)

1368

1265

+++)

1397

1425

1170

1697

1336
1152

II

93.9 '

91.8 ^:

92.6 ^:

92, Ο '

92.4

94.9

94.0

92.2

93.4

92.5

95.3

91.6

92.9

93.0

95.1

94.2 '

94.2 '

95.3

Toluene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer)

6.2

Sodium bromide 1.9

1221

94.0

Dimethylthioform
amide 3.0 Sodium bromide 2.5 1146 93, O ¹ It Ethylene carbonate 3.1 Sodium chloride 2.5 ¹ no agglomeration, no
in a polymerization
checked ⁷ H Ethylene carbonate 3.1 1-eicoses 3.8 ¹ Il Il Tetramethylgua
nidin 4.2 Sodium bromide Il Il Methyl carbamate 2.7 Sodium bromide 3.3 ² Il 92.9 ¹ O Methyl carbamate 2.6 1-eicoses 4.7 ² Il Agglomeration co
OO Dimethylacetamide 3.0 without - 1256 2
Agglomeration ro
cn Dimethylacetamide 3.5 1-eicoses 2.6 50% 91, 6 ¹ O Dimethylacetamide 2.9 Triton X-100
■ ++++) 2.1 75% 2
Agglomeration Benzonitrile 3.4 without - 1097 94.4 ¹ co γ-butyrolactone 6.2 without - 98% 2
Agglomeration γ-butyrolactone 6.1 without - 1154 2
Agglomeration Dimethylformamide 2.7 without - 90% 93.9 ² Dimethylformamide 2.4 Stearic acid
amide 1.8 100% 92.1 ¹ D imethylformamide 2.5 without - 1600 N-methyl pyrrolidone 3.5 without _— 1507

(CgH ₅ ) ₃ P0 9, 1 1-excoses Ethylene carbonate 3, 1 without Ethylene carbonate 3, 1 iodine

2.7 90% agglomeration ²

1088 93, O ¹

2.3 80% agglomeration

+) based on the titanium (III) chloride material

++) based on the electron pair donator

+++) Average value from two test polymerization approaches

++++) Octylphenoxypolyethoxyethanol (Rohm and Haas)

-J 1) grinding in a laboratory ball mill, which is equipped with 875 g grinding balls with a diameter

C ₀ knife of 1 cm each is loaded.

^ _n 2) Ground in a laboratory ball mill with a charge of 1750 g grinding balls, ■ * - * each having a diameter of 1 cm.

CD
CD
■ P-CO

Cn - ~ J CD

Example 7

The influence of an increase in the proportion of electron pair donor and agglomeration suppressor is shown. Higher Portions of the electron pair donor require higher proportions of the agglomeration suppressor, as the attractive forces between the titanium (III) chloride particles coated with the electron pair donor. For demonstration of these influences, HMPT is used as an electron pair donor and octamethylpyrophosphoric acid amide (OMPA) as an agglomeration suppressor. It is in the example 1 Proceed as described and 2, but with the modification that instead of the ball mill used in Example 1 the mill described in US Pat. No. 3,688,992 is used with a higher comminution rate. The mill is loaded with 90.7 kg grinding balls with a diameter of 12.7 mm each. It comes with one revolution ground for 285 min. The results obtained are shown in Table IV.

Table IV

% HMPT % 0MPA activity Agglomeration 1266 II 0 4.5 0.2 1318 1184 94, 6.5 0.3 3 6.2 1.1 93, 4th 6.2 2.7 94, Example 8

This example shows that only small amounts of an ionic agglomeration suppressor (AC) are required to prevent agglomeration of a powdery titanium (III) chloride / electron pair donor mixture. The results are shown in Table V.

709825/0949

Table V

ED% by weight ED +) AC% by weight AC ++) activity +++) II

HMPT 6.3 triethylamine 0.9 1482 93.2

hydrochloride

Dimethyl

acetamide 2.9 sodium chloro 2.2 1368 92.5

rid

_o +) based on the weight of the titanium (III) chloride material

++) based on the weight of the electron pair donor

n> +++) occurs depending on the grinding conditions and grinding device

-v. an agglomeration visible to the naked eye in the absence of f,

_{(O of} the agglomeration suppressor.

Example 9

This example is intended to show that already relatively low Additions of polarizable agglomeration suppressors bring about effective suppression of agglomeration capital. The results are summarized in Table VI.

09826/0949

Table VI

ED

Wt% ED

1)

AC

% By weight AC ²⁾ activity ³⁾

II

-j ο co

HMPT

Dimethylformamide

Dimethylacetamide

Benzonitrile

N-methyl-pyrrolidone

5.8

2.2

.5.0

3-5

Propionamide

14-heptacosanone

Iodine lauron

1-eicoses

1.0

2.0

1.5

2.0

1252

111 * 5

1300

(M

(M

(M

11 * 25

95

93. J »92.1 *

93.0

1) based on the weight of the titanium (III) chloride material

2) based on the weight of the electron pair donor

3) in the absence of the agglomeration suppressor, agglomeration occurs
depending on the grinding device and the grinding parameters

4) Average values from two test polymerizations

Cn -J CD

Example 10

In this example, the impact of the crushing speed on the degree of agglomeration is present an agglomeration suppressor shown. The tendency to agglomerate increases with higher levels of agglomeration suppressors decreases and increases with higher shredding speeds. The ones in the table below VII data shown under experiment no. 2 can be clearly seen as the first beginning of those in experiment no. 4 Interpret agglomeration.

In this context it should be pointed out again that Berry et al. (Ie) the comminution rate R as a function of the surface area of the grinding media, for example the grinding balls in a ball mill, depending on the weight of the material to be ground. The grinding speed is also dependent on the size of the grinding media and the diameter of the mill. With various types of crushers and mills, it is often difficult to accurately predict the crushing speed R. Thus, the characterization of the grinding speed of different types of grinding equipment can often only be determined empirically for a given set of grinding conditions. Conventional laboratory ball mills, such as that used in Example 1, are referred to as "slow" in the context of this description with regard to the comminution rate. Larger devices, such as those described in US Pat. No. 3,688,992 and which can be operated at different speeds, are referred to as "medium-fast ^{11" or "fast" with regard to the comminution speed, depending on the speed set} is used, contains 875 g grinding balls with a diameter of 1 cm. The mean speed for the grinding device according to US Pat. No. 3,688,992 is

-1 -1

145 min, the fast speed 285 min. The energy

709825/0949

consumption for the mean speed is 6 A and the high speed at 7.5 A. The crushing device according to US Pat. No. 3,688,992 is 90.7 kg grinding balls with a Loaded with a diameter of 12.7 mm each, both for the medium and for the high speed.

709825/0949

Tabel VII Wt%
OMPA Temp. Shredding
speed activity II 93.6 attempt
No. Wt%
HMPT 0.2 50 ⁰ C. slow (48 h) 1318 94.0 Agglomeration (after 3 h)
1355 94.7 1 4.5 0.3 50 ⁰ C. medium (12 h) 405 93.0
(beginning agglomies
ration) 2 4.5 0.6 50 ⁰ C medium (12 h) 1133 -J 3 4.5 0.3
0.6 50 ⁰ C
50 ⁰ C fast (7 h)
fast (7 h) ) 9825, 4th
5 4.5
4.5 / 0949

Example! 11 (comparative example)

In Table VIII are a number of ineffective agglomeration suppressors in addition to the substances already marked with an asterisk in Table I. compiled. The substances compiled in Table VIII were also used in the examples 1 and 2 processed and checked. In all cases, hexamethylphosphoric triamide serves as an electron pair donor. The compounds listed in Table VIII were not tested in experimental polymerizations.

Table VIII

Sodium trimetaphosphate toluene

kappa-carrageenan ammonium dihydrogen phosphate sodium acetate 12-anisaldehyde 2-undecanone Teflon ^{1 1} K-IO fluorinated polymer

PO

Magnesium oxide dodecyltrimethylammonium diphenyl phosphate

Methyl amyl ketone 0

NH

; PN Cn-Pr) ₂

Sulfanilamide

709825/0949

Di-n-propyl disulfide pentaerythritol

Titanium oxide phosphorus pentoxide

Isoquinoline thorium oxide

(C ₃ H ₇ O ₂ ) ₂ Ti0

Example 12 (/ comparison example)

In this example there are a number of combinations of an electron pair donor and an agglomeration suppressor compiled, which are treated and investigated in the manner described in Examples 1 to 3. From the Apart from the control experiment, agglomerations are observed in all cases. The ineffectiveness of the combinations is due to the large excess of electron pair donors which leads to the formation of a stronger than a monomolecular adsorption layer. Under use of the abbreviations used in Table III are the results obtained for this comparative example in Table IX summarized.

709825/0949

Table IX Wt% +) AC Wt .-% ++) Degree of agglomeration % ED 6.14 - - > 90 % Isopentyl ether 5.79 iodine 1.14 > 90 % Isopentyl ether 6.22 iodine 1, 44 > 90 % Pyridine 6.25 - - 98 % γ-butyrolactone 5.8 iodine 1.2 about 90 Agglomeration +++) Trilauryl
trithiophosphite 5.7 Silicon dioxide 0.9 no % -J Trilauryl tri-
thiophosphite 6.1 iodine 1.0 about 25 % · co
GO γ-butyrolactone 6.04 Triethylamine
hydrochloride 0.8 about 80 25 / Isopentyl ether 6.1 __ _ » 100% CD
CO N, N-dimethyl
formamide 6.1 Propionamide 1.03 95% co Pyridine 6.29 Sodium chloride 0.96 95% Pyridine 6.16 Propionamide 0.88 90% > ++) γ-butyrolactone 5.8 Sodium chloride 1.08 5-10 p γ-butyrolactone

+) based on the weight of the titanium (III) chloride material

++) based on the weight of the electron pair donor

+++) when tested according to Example 2, an activity of 1195 and an isotactic index of 91.2 are obtained

++++) activities of 1153 and 1431 and isotactic indices of 96.0 and 93.8, respectively, are obtained Degree of agglomeration is determined visually.

Example 13 f / comparison example)

In this example, for comparison purposes, are the effects different agglomeration suppressors shown on selected electron pair donors. The ineffective combinations are in turn due to the presence of an excess of electron pair donors and / or agglomeration suppressors traced back. The data are summarized in detail in Table X.

09825/0941

Table X

ED conζ.

(ED = γ-butyro-

lactone)

AC

.41.

AC Conc,

Agglomeration

6.08 6.1 6.2 5.8 6.0 6.2 6.2 6.0 6.0 6.0

iodine 1.0 98- Propionamide 0.88 . 25th sodium 90 chloride I.08 sodium 1.8 • 5-10 chloride 95 Silicon 1.0 dioxide l.fc 75 OMPA +) 3-0 50 OMPA 95 sodium 1.0 chloride 1.0 75 Lauron 80

(ED = pyridine)

= (CH ₃ ) 3PS)

Iodine propionamine

Sodium chloride

1.1 »

58

95 95

—— 17th - - 50 Silicon
dioxide 1.2 60 sodium
chloride 2.0 60

709825/0949

(ED = isopropyl ether)

• ♦ 3,

Iodine 1, 1

Triethyl-0.9

amine hydro

chloride

OMPA 1.2

> 90
80

90

(ED = dimethylformamide)

6.1 - 6.0 sodium
chloride (ED = triethyl
amine) 6.1 - 6.0 OMPA (ED = n-butyl
ether) 6.0 - 6.1 OMPA Example 14

0.8

1.2

1.2

100 100

100 100

100 100

It is shown that a change in milling conditions in a particular electron pair donator causes agglomeration can trigger. A TiCl., - composition is also used a TiClg / electron pair donor composition and with compared to a composition that TiClο »an electron pair donator and contains an agglomeration suppressor. With the results shown in Table XI is the agglomeration by seven of the milled catalyst component compositions certainly. As an indication

709825/0949

An effective agglomeration suppression is considered when the percentage of particles that have a grain size of less than 75 μm in the composition increases. In all experiments, benzophenone is used as an electron pair donor and sodium bromide as an agglomeration suppressor. The procedure described in Example 1 is repeated, except that 1750 g of grinding balls are used having a diameter of 1 cm and that a grinding temperature is maintained of 55 ⁰ C, since preliminary tests have shown that benzophenone not at a milling temperature of 50 ⁰ C Shows agglomeration. The polymerization and the determination of the activity and the isotactic index are carried out in the manner described in Example 2. All data for activity and isotactic index are averages from two test polymerizations.

709825/0949

Table XI

Wt .-% wt .-% benzophenone NaBr

Grain size distribution activity

II

(%> 150 μπι) (% 75-150 μπι) (% < 75 nm)

9 8th 83 11 6th 83 ---- 6th 9 85 5 13th 82 CD
(D 6th 8th 86 OO 6th ———— KJ
cn 6th 55 10 35 O 6th 2.9 46 9 45 CD
-P- 31 5 64 CO 6th 2.9 6th 3.9 15th 6th 79 6th 3.9 25th 4th 71 13th 5 82

91.5 90.7 91.6

95.2 94.8 95.3
92.7
95.3 94.9 ^]

1075

1266

1166

1114

572

959

890

1025

830

1078 ^:

1 ) Average value from three test polymerizations

Claims (1)

Claims 1. Agglomeration-free finely divided catalyst component, obtained by crushing the following three starting products together: a) a titanium (III) chloride, b) an electron pair donator in sufficient quantity Improvement of the stereospecificity or the stereospecificity and the activity of the catalyst component and c) an agglomeration suppressor in one for practically complete suppression of an agglomeration sufficient amount in the catalyst component. 2. Catalyst component according to claim 1, characterized characterized in that the titanium (III) chloride is a product obtained by one of the following processes obtained: (a) reduction of titanium (IV) chloride with a metal, (b) reduction of titanium (IV) chloride with Hydrogen, (c) reduction of titanium (IV) chloride with an organometallic compound and (d) comminution of titanium (III) chloride with a halide of a metal of the third group of the periodic table. 3. Catalyst component according to one of claims 1 or 2 characterized in that a titanium (III) - 709825/0949 2 6 b 7 9 1 Chloride is used, which is obtained by reducing titanium (IV) chloride was obtained with aluminum. 4. Catalyst component according to claim 3, characterized in that the concentration of the Electron pair donor based on the titanium (III) chloride material Is 2 to 15 wt%. 5. Catalyst component according to claim 3, characterized in that the concentration of the Electron pair donor based on the titanium (III) chloride material Is 2.5 to 10 wt%. 6. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a substance that controls the interaction forces acting between the particles of the composition modified or a polarizable substance that adsorbs to the particles of the composition a creates steric hindrance that does not allow the particles to touch one another. 7. Catalyst component according to claim 6, characterized in that it is characterized that the agglomeration suppressor is one of the following ionic compounds: an ionic salt of a metal of the first or the second main group of the periodic table or one 709825/0949 Transition metal; a quaternary ammonium salt of the general chemical formula RN X, where R is a hydrogen atom, an alkyl radical or an aryl radical and X is a halogen anion or the sulfate radical; ionic surfactants; the finely divided, water-soluble ammonium salt of an amidopolyphosphonate, which is obtained from P ₂ Or ^and anhydrous ammonia by reaction in the dry vapor phase; Salts of aliphatic triacids and their hydroxyl-substituted derivatives; Alky / alkali metal sulfates; Alkaline earth metal phosphates; Alkaline earth metal titanates and non-gaseous halogens. 8. Catalyst component according to claim 6, characterized in that the agglomeration ^ suppressor is one of the following polarizable substances: Compounds of the general chemical formula (A) ₂ P (O) OP (O) (A) ₂ , where the remainder A is the Has meaning OR, NRR ¹ or OH and R and R ^{1 are} each an alkyl radical and this meaning applies with the proviso that at least one of the radicals A has the meaning OR or NBH ¹ , trialkyl phosphates of the general chemical formula (RO), PO, where R is an alkyl radical; polymeric silicon compounds, and though
iamorphic silica and siloxanes; Dialkyl phosphoric acids of the general chemical formula (RO) ₂ P (O) OH, where R is an alkyl radical; Dialkyl maleate and dialkyl fumarates; by reacting (C ₆ Hc) ₂ Si (OH) ₂ and a titanate of the general chemical formula Ti (OR) . received 70982B / 0949 Reaction product where R is an alkyl radical; Compounds of the general chemical formula RCGKfH ₂ , in which R is an alkyl radical with 1 to 18 carbon atoms, and their polymers; a solid element, namely graphite, amorphous carbon, or sulfur; Strength; Alkyl ketones with the proviso that the number of all carbon atoms in the two alkyl radicals is in the range between 20 and 30 inclusive; Epoxides and their polymeric derivatives; Trialkyl borates; Urea and alkyl substituted ureas; Alkylenediaminetetraacetic acids; water soluble cellulose ethers; Phthalocyanine pigments; Acrylic acid esters having 1 to 4 carbon atoms in the alcohol component; Compounds of the general chemical formula (PNX-), where X is a chlorine atom or a bromine atom and η is a number from 2 to 4; Compounds of the general chemical formula (C ₆ H _1. , J ₃ SnSP (S) (OR) ₂ or ((C ₆ H ₁ ^ 3Sn) ₂ S where R is an alkyl radical having 1 to 6 carbon atoms, and the non-gaseous α-olefins. 9. Catalyst component according to claim 3, characterized by a proportion of the agglomeration suppressor of 0.1 to 5 wt .-%, based on the Weight of the electron pair donor. 709825/0949 TO. Catalyst component according to Claim 3, characterized by a proportion of the agglomeration suppressor in the range from 0.6 to 3.0% by weight, based on on the weight of the electron pair donor. 11. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is an ionic salt of a metal in Group IA of the Periodic Table of the Elements. 12. Catalyst component according to claim 1, characterized in that the agglomeration suppressor is an alkali metal halide. 13. Catalyst component according to claim 12, characterized in that the agglomeration suppressor Is sodium bromide or sodium chloride. 14. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is an alkali metal benzene sulfonate or an alkali metal alkyl sulfonate, the alkyl radical of the alkyl sulfonic acid Has 1 to 20 carbon atoms. 15. Catalyst component according to claim 14, characterized in that the agglomeration suppressor Is sodium benzene sulfonate. 709825/0949 16. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is an ionic salt of a metal from group HA of the Periodic Table of the Elements. 17. Catalyst component according to claim 3, characterized in that that the agglomeration suppressor is an ionic transition metal salt. 18. Catalyst component according to claim 17, characterized in that the agglomeration suppressor Is copper stearate or zinc stearate. 19. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a quaternary ammonium salt of the general chemical formula R ₄ NX, wherein the radical R is a hydrogen atom, an alkyl radical or an aryl radical. 20. Catalyst component according to claim 19, characterized in that the agglomeration suppressor a trialkyl hydrochloride, trialkyl hydrobromide or trialkyl hydroiodide with 1 to 4 carbon atoms in the alkyl radical is. 21. Catalyst component according to claim 20, characterized in that the agglomeration suppressor Is triethylamine hydrochloride. 709825/0949 22. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is the water-soluble ammonium salt of an amidopolyphosphonate, which is obtainable by reaction from the dry vapor phase of P ₂ ^ s ^m ^ anhydrous ammonia. 23. Catalyst component according to claim 3, characterized in that it is known shows that the agglomeration suppressor is an alkali metal salt, an alkaline earth metal salt or a transition metal salt of an aliphatic triacid is. 24. Kalalysatorkomponente according to claim 23, characterized in that the agglomeration suppressor Calcium citrate or iron (III) ammonium citrate is. 25. Catalyst component according to claim 3, characterized in that g e code It means that the agglomeration suppressor is an alkyl alkali metal sulfate. 26. Catalyst component according to claim 25, characterized in that the agglomeration suppressor is g e k e η η ze i c hn e t Dodecy! Sodium sulfate is. 27. Catalyst component according to claim 3, characterized in that the agglomeration sub- 709825/0949 pusher is an alkaline earth metal phosphate. 28. Catalyst component according to claim 27, characterized in that the agglomeration suppressor tribasic calcium phosphate. 29. KataIysatorkomponente according to claim 3, characterized in that the agglomeration suppressor is an alkaline earth metal titanate. 30. Catalyst component according to claim 29, characterized in that the agglomeration suppressor Calcium titanate is. 31. Catalyst component according to claim 1, characterized in that the agglomeration suppressor is a non-gaseous halogen. 32. Catalyst component according to claim 31, characterized in that the agglomeration suppressor : Iodine is. 33. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a substance of the general chemical formula (A) ₂ P (O) OP (O) (A) ₂ , where the radical A has the meaning OR, NRR ¹ or OH and R and R ^{1 are} each an alkyl radical with 1 to 4 carbon atoms, with the proviso 709825/0949 that at least one of the radicals A is either OR or NRR ¹ , 34. Catalyst component according to claim 33, characterized in that the agglomeration suppressor is octamethylpyrophosphoric acid amide or acid Is dimethyl pyrophosphate. 35. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a trialkyl phosphate of the general chemical formula (RO) ₃ PO, in which R is an alkyl radical with 1 to 6 carbon atoms. 36. Catalyst component according to claim 35, characterized in that the agglomeration suppressor Is tributyl phosphate. 37. Catalyst component according to claim 3, characterized in that the agglomeration suppressor a polymeric silicon compound is, namely an amorphous silica or a siloxane. 38. Catalyst component according to claim 37, characterized in that the agglomeration suppressor is an amorphous colloidal silica whose particles form chain-like formations sintered together, and a grain size in the range -3 -3
of about 7 · 10 to 14 · 10 μπι have that the agglomeration 709825/0949 '/ IC meration suppressor hexamethylsiloxane or polydimethyl is siloxane. 39. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a dialkyl phosphoric acid of the general chemical formula (RO) ₂ P (O) OH, in which the radical R is an alkyl radical with 1 to 6 carbon atoms. 40. Catalyst component according to claim 39, characterized in that the agglomeration suppressor Diisoamy! Phosphoric acid is. 41. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a dialkyl maleate or a dialkyl fumarate with 1 to 4 carbon atoms in the alkyl radical. 42. Catalyst component according to claim 41, characterized in that the agglomeration suppressor Is diethyl maleate. 43. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is the reaction product of a substance of the formula (CgHc) 2 ^Si (OH) 2 ^{un (} ^ a titanate of the general chemical formula Ti (OR) ₄ , where the radical R is an alkyl radical having 1 to 4 carbon atoms. 709825/0949 - / 14. 44. KataIysatorkomponente according to claim 3, characterized in that the agglomeration suppressor _{is a substance of the general chemical formula RCONH 2} , in which R is an alkyl radical with 1 to 18 carbon atoms, or a polymeric alkyl amide. 45. Catalyst component according to claim 44, characterized in that the agglomeration suppressor Propionic acid amide, stearic acid amide or polyacrylic acid amide is. 46. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a solid element, namely graphite, amorphous carbon or sulfur. 47. Catalyst component according to claim 3, characterized in that the agglomeration suppressor Strength is. 48. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is identified is a dialkyl ketone having 20 to 30 total carbon atoms in the two alkyl groups. 49. Catalyst component according to claim 48, characterized in that the agglomeration sub- 709825/0949 pusher is lauron or 14-heptacosanone. 50. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is an epoxy or a polymeric epoxy derivative. 51. Catalyst component according to claim 50, characterized in that the agglomeration suppressor is the diepoxide of cyclohexenylmethyl cyclohexene carboxylate or polyethylene oxide. 52. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a trialkyl borate having 1 to 4 carbon atoms in the alkyl radical. 53. Catalyst component according to claim 52, characterized in that the agglomeration suppressor Is trimethyl borate. 54. Catalyst component according to claim 3, characterized in that the agglomeration suppressor Is urea or an alkyl-substituted urea, the alkyl radical having 1 to 4 carbon atoms. 55. Catalyst component according to claim 54, characterized in that the agglomeration suppressor Is urea or tetramethylurea. 709825/0949 56. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is an alkylenediamine tetraacetic acid with 2 to 4 carbon atoms in the alkylene radical. 57. Catalyst component according to claim 56, characterized in that the agglomeration suppressor Is ethylenediaminetetraacetic acid. 58. Catalyst component according to claim 3 / characterized in that the agglomeration suppressor is a water-soluble cellulose ether. 59. Catalyst component according to claim 58, characterized in that that the agglomeration suppressor is methyl cellulose or sodium carboxymethyl cellulose is. 60. Catalyst component according to claim 3, characterized in that the agglomeration suppressor Is phthalocyanine, copper phthalocyanine, chlorinated copper phthalocyanine or sulfonated copper phthalocyanine. 61. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is an acrylic acid ester having 1 to 4 carbon atoms in the alcohol part. 709825/0949 62. Catalyst component according to claim 61, characterized in that the agglomeration suppressor Is methyl acrylate. 63. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a substance of the general chemical formula (PNX) in which X is chlorine or bromine and η is 2 to is. 64. Catalyst component according to claim 3, characterized in that the agglomeration suppressor a substance of the composition (OR) ₂ or where the radical R is an alkyl radical having 1 to 6 carbon atoms. 65. Catalyst component according to claim 3, characterized in that the agglomeration suppressor is a non-gaseous α-01efin. 66. Catalyst component according to claim 65, characterized in that the agglomeration suppressor 1-eicosen is. 709825/0949 67. Catalyst component according to claim 3, characterized in that the titanium (III) chloride material is obtained by reducing titanium (IV) chloride with aluminum, the electron pair donor benzophenone and the agglomeration suppressor is sodium bromide. 68. Catalyst component according to claim 3, characterized in that the titanium (III) chloride material is produced by reducing titanium (IV) chloride with aluminum, the electron pair donator Triphenylphosphine oxide and the agglomeration suppressor is sodium bromide. 69. Use of the catalyst component according to one of claims 1 to 68 as a catalyst in conjunction with an alkyl aluminum compound. 70. Process for polymerizing α-olefins in the presence a catalyst containing titanium (III) chloride and an alkylaluminum compound, characterized in that that first the titanium (III) chloride material with an electron pair donator in one for improvement the stereo specificity or the stereo specificity and the activity of the catalyst sufficient amount in the presence of an agglomeration suppressor in a crushed sufficient amount for practically complete suppression of the agglomeration of the catalyst and is milled before the titanium (III) chloride material 70 9 8 25/0949 is added to the polymerization process. 709825/0949