DE3244871A1 - METHOD AND CATALYST COMPONENT FOR PRODUCING POLYOLEFINES - Google Patents

Description

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DEA-13 732

Process and catalyst component for the production of polyolefins

The invention relates to a method for the production of Polyolefins using a new polymerization catalyst.

In this field of technology are catalysts consisting of a magnesium halide and one coated thereon transition metal compound such as titanium compound is known from Japanese Patent Publication No. 12105/1964 and catalysts made by the co-grinding of a magnesium halide and titanium tetrachloride are described in Belgian patent 742 112.

In the manufacture of polyolefins, however, it is desirable that the catalyst activity be as high as possible, and from this point of view, the method described in Japanese Patent Publication No. 1215/1964 is still unsatisfactory, since it leads to low polymerization activity, while in the case of that described in BE-PS 742 112 Processes the polymerization activity quite a bit

is high but still needs further improvement.

According to DE-PS 2 137 872, the amount of used is Magnesium halide is significantly reduced by the fact that it is used together with titanium tetrachloride and aluminum oxide is pulverized; a notable increase in activity per solid that acts as a guide to productivity can be viewed, but cannot be seen, so a higher activity catalyst would be desirable.

In the production of polyolefins it is also important in terms of productivity and handling Slurry, it is desirable that the bulk density of the polymer formed is as high as possible. Considering this point of view is in the method described in Japanese Patent Publication 12 105/1964 the bulk density of the formed polymer is low and the polymerization activity is unsatisfactory. On the other hand, in the case of the one described in BE-PS 742 112 Process, although the polymerization activity is high, the bulk density of the polymer formed is low, so that further improvements are desirable.

The invention is therefore based on the object of providing a new polymerization catalyst, with the help of which the disadvantages explained above can be avoided. This new catalyst is said to be high Show polymerization activity, lead to the formation of a high bulk density polymer in high yield and a allow extremely easy implementation of a continuous polymerization process. With the help of this Catalyst, a process for homopolymerization or copolymerization of olefins is to be carried out.

The object of the invention is thus a solid component

r - 'I ■'

a catalyst for homopolymerization or copolymerization of olefins, which consists of a substance, which can be obtained by reacting at least one of the following four components:

(1) a compound of the general formula R (OR) MgX "_ _,

(2) a compound of the general formula

Me (OR ³ ) X,
P z ~ p

(3) a compound of the general formula

₆ I ₇

R - (- Si-O -} - R

I ^q
R ^{5 and}

(4) a halogen-containing titanium compound

12 3 7 where in the formulas R, R, R and R each one Hydrocarbon radical with 1 to 24 carbon atoms,

4 5 6
R, R and R each represent a hydrocarbon radical having 1 to 24 carbon atoms, an alkoxy group, a hydrogen atom or a halogen atom, X a halogen atom, Me an element from Groups I to VIII of the Periodic Table of the Elements, excluding silicon and titanium, ζ the valence of Me and m, η, ρ and q are in the following relationships: O = m = 2, O = n <2, 0 <m + n = 2, 0 <ρ = z, 1 = q = 30.

The invention also relates to a method for Production of polyolefins by homopolymerization or copolymerization of olefins in the presence of a catalyst, comprising a solid catalyst component and an organometallic bond. This procedure is through characterized in that the ieate catalyst component consists of :; consists of a substance obtainable by reacting at least the following four components

(1) a compound of the general formula

^Ri _m ^(OR2) n ^M 5 ^X 2-m-n '

(2) a compound of the general formula

Me (OR ³ ) X

P z-P

(3) a compound of the general formula

6 '7

R - (- Si-O -) - R

I ^q

> 5 and

(4) a halogen-containing titanium compound

12 3 7 where in the formulas R, R, R and R each one Hydrocarbon radical with 1 to 24 carbon atoms,

45 ς
R, R and R each represent a hydrocarbon radical having 1 to 24 carbon atoms, an alkoxy group, a hydrogen atom or a halogen atom, X a halogen atom, Me an element of groups I. to VIII of the Periodic Table of the Elements, excluding silicon and titanium, ζ the Valence of Me is and m, η, ρ and q are in the following relationships: 0 = m = 2, O = η <2,. 0 <m + n = 2, 0 <ρ = z, 1 = q = 30.

The catalyst according to the invention shows an extraordinary one high polymerization activity and, as a result, the partial pressure of the monomer during the polymerization at kept low values. In addition, the bulk density of the polymer formed is so high that the production efficiency can be improved. In addition, the amount of catalyst that is present in the polymer formed according to, 5 Completion of the polymerization remains so low that in the polyolefin production process, the stage to remove the catalyst can be omitted, thereby simplifying the work-up process for the polymer is made possible and polyolefins overall in extraordinary

32AA871

can be produced economically. '

In the method according to the invention, the amount of Polymers, the pr <^ unit of the polymerization reactor is formed large because of the high bulk density of the polymer.

The invention has the further advantage that in the particle size distribution of the polymer formed the proportion of coarse particles and fine particles below 50 μπι despite the high bulk density is low and that, as a result, it is not only easy to carry out a continuous polymerization reaction but also easy to handle the polymer particles, for example in centrifugal separation during the work-up process for the polymer and during the transport of the powdered polymer.

Another advantage of the invention can be seen in the fact that prepared with the aid of the catalyst according to the invention Polyolefins, as already mentioned, have high bulk density and that polyolefins with the desired Melt index can be obtained at a lower hydrogen concentration than with conventional processes, which enables is that the total pressure is kept at a relatively small value during the polymerization. This, too, results in extraordinary improvements in terms of economy and productivity achieved.

In addition, the olefin absorption rate decreases with the passage over time not so strongly in the case of the polymer J sat ionsvfrf «their ι · π for olefins using the he Γ indunqsqomälien K.it.ilysators and therefore the polymerization can last for a long time

yo-

Duration can be carried out with a smaller amount of the catalyst.

In addition, polymers prepared using the catalyst of the present invention have excellent properties narrow molecular weight distribution and its hexane extract is low, indicating that the Formation of low quality (low molecular weight) polymers is kept low. This is how it is, for example in the production of film quality possible to get good quality products Possess superior anti-blocking properties and other properties.

With the help of the invention, a new catalyst system made available, the numerous such characteristic Has features and is able to avoid the disadvantages of the prior art explained above. It is very surprising that these features can be achieved in a simple manner with the aid of the catalyst according to the invention wiTclon.

The invention is described below on the basis of preferred embodiments.

ι τ

Compounds of the formula R ^v (OR) MgX "_ _ used in the present invention, substantially any compounds of this formula can be used, in which

1 2
R and R each represent a hydrocarbon radical having 1 to 24 carbon atoms. However, they are particularly preferred

1 2
Compounds in which R and R each represent an alkyl group. Examples of such compounds include diethyl magnesium, diisopropyl magnesium, di-n-butyl magnesium, di-sec-butyl magnesium, methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium

iodide, n-propy! magnesium chloride, n-buty! magnesium chloride, n-butylmagnesium bromide, sec.-butylmagnesium chloride, phenylmagnesium chloride, Decyl magnesium chloride, methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, n-butoxymagnesium chloride, n-octoxymagnesium chloride, methylmagnesium methoxide, Ethyl magnesium ethoxide, n-butyl magnesium ethoxide, sec-butyl magnesium ethoxide and decyl magnesium ethoxide. Complexes with a trialkylaluminum can also be used, for example a complex of di-n-butyl- · magnesium and triethyl aluminum.

As compounds used according to the invention of the general

3
my formula Me (OR) X can use different connec-

P zP
fertilizers are mentioned, such as NaOR, Mg (OR ³ ) ₂ , Mg (OR ³ ) X, Ca (OR ³ ) ₂ , Zn (OR ³ ) ₂ , ZnCOR ³ ) X, CdCOR ³ ) ₂ , A1COR ³ ) ₃ , A1 (OR ³ ) ₂ X, BCOR ³ ) ₃ , BCOR ³ ) ₂ X, Ga (OR ³ ) ₃ , Ge (OR ³ ) _4> SnCOR ³ ) _A , PCOR ³ ) ₃ , CrCOR ³ ) ₂ , MnCOR ³ ) _v Fe (OR ³ ) _v FeCOR ³ ) ₃ , CoCOR ³ ) ₂ ,

3 3

and Ni (OR) "where in the formulas R can essentially stand for any hydrocarbon radical with 1 to 24 carbon atoms, with alkyl and aryl groups being particularly preferred. Preferred examples of such compounds include NaOC ₂ H ₅ , NaOC ₄ H ₉ , MgCOGH ₃ ) ₂ , MgCOC ₂ H ₅ ) _2> MgCOC ₃ H ₅ ) _2>

CaCOC ₂ H ₅ ) ₂ , ZnCOC ₂ H ₅ ) ₂ , ZnCOC ₂ H ₅ ) Cl, AlCOCH ₃ ) ₃ AiCOc ₃ H ₇ ) ₃ , AiCOC ₄ Hg) ₃ , AiCOC ₆ H ₅ ) ₃ , BCOC ₂ H ₅ ) ₃ , BCpC ₂ H ₅ ) ₂ ci, PCOC ₂ H ₅ ) ₃ , PCOC ^ H -) -, and Fe (OC ₄ H ₉ ). Compounds of the general formulas are particularly preferred for the purposes of the invention

Mg (OR ³ ) X_, Al (OR ³ ) X ₁ and B (OR ³ ) X-. , wherein as radicals 3 -Έ> 2-p ρ 3-p. ρ 3-p

R alkyl groups with 1 to 4 carbon atoms and phenyl groups are particularly preferred.

BATH ORIGINAL

In the compounds of the all common formula

R ⁶ -4- Si-O -} R ⁷

The radicals R, R and R can represent hydrocarbon radicals having 1 to 24 carbon atoms, alkoxy groups, hydrogen atoms or halogen atoms, with alkyl, aryl, alkoxy groups and halogen atoms being preferred, and R may any hydrocarbon radical having 1 to 24 carbon atoms with alkyl and aryl groups being preferred.

Examples of such compounds include monomethyltrimethoxysilane, Monomethyltriethoxysilane, monomethyltrin-butoxysilane, Monomethyltri-sec.-butoxysilane, monomethyltriisopropoxysilane, Monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, Dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, Trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, Monomethyldimethoxymonochlorosilane, Monomethyldiethoxyinonochlorsi.lan, Monomethylmonoathoxydichlorosilane, monomethyldiethoxymonochlorosilane, Monomethyldiethoxymonobromosilane, monoethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, Monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyltriphenoxysilane, Diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, Triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, Monoethyldiethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, Mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, Mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, Diphenyldiothoxysilane, Diphenylmonoethoxy-

monochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, Monoisopropoxytrichlorosilane, mono-n-butoxy trichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, Monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono-p'-methylphenoxytrichlorosilane, dimethoxydichlorosilane, Diethoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydi ^ chlorosilane, dioctoxydichlorosilane, Trimethoxymonochlorosilane, triethoxymonochlorosilane, Triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, Tri-sec-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane, and also chain-like or cyclic polysiloxanes with recurring units of the formula

R ⁴

-f- Si-O -h— ■ -

obtained by condensation of the above compounds.

Halides and alkoxy halides of titanium can be used as halogen-containing titanium compounds which are suitable for the purposes of the invention. Preferred titanium compounds are compounds of tetravalent and trivalent titanium. Preferred examples of tetravalent titanium compounds include compounds of the general formula Ti (OR) X, in which R is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and r is a number corresponding to the relationship 0 = r <4 such as titanium tetrachloride, titanium tetrabromide, Tit-antetraiodid, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, Mo nopentoxytrich lortitan, Monophenoxytrichlortitaf

BATHROOM «3INAL

Diphenoxydichlorotitanium and triphenoxymonochlorotitanium. as suitable trivalent titanium compounds are titanium trihalides to be mentioned, which by reduction of titanium tetrahalides, such as titanium tetrachloride and titanium tetrabromide, with hydrogen, aluminum, titanium or an organometallic compound of a metal from group I bis III of the Periodic Table of the Elements are formed, as well as trivalent titanium compounds obtained by reduction of tetravalent alkoxy titanium halides of the general formula Ti (OR) .X. with an organometallic compound one Metal of groups I to III of the Periodic Table of the Elements are formed, where in the formula R is an alkyl, Aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and s is a number according to the relationship 0 <s <4 mean. Tetravalent titanium compounds are most preferred in the present invention.

In practicing the invention, the method of preparing the solid catalyst component by reaction is subject to (1) a component of the general formula

12th

R (OR) X ", (2) a component of the general m η 2-m-n

Formula Me (OR) X, (3) a compound of the general ρ ζ ρ

formula

₆ I ₇

R -f- Si-O-} - R

and (4) a halogen-containing titanium compound, none special restriction. The ingredients (1) to (4) can be heated to a temperature in the range of 20 to 400 ° C, preferably from 50 to 300 ° C, for a time normally in the range of 5 minutes to Hours lies 'in the presence' or absence of an inert

Solvents are reacted with one another or can by a treatment of co-milling (copulveriöutioneboharull uricj) or by one; c. | epitjnetc3 combination these methods are implemented. The keihoniolge of the Implementation of the components (1) to (4) is also not specifically specified. The four components can be reacted at once or three of the components can be reacted, after which the reaction with the Remaining other constituent takes place or two of the constituents can also be implemented, after which the Reaction with one of the remaining two components and then the reaction with the remaining component he follows.

Inert solvents which can be used in the reaction described above are not subject to any special restriction. Usually you can use hydrocarbon solvents and / or hydrocarbon derivatives that do not inactivate Ziegler catalysts lead to be used. Examples of such solvents include various saturated aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic ones Hydrocarbons such as propane, butane, pentane, hexane, Heptane, octane, benzene, toluene, xylene and cyclohexane, as well as alcohols, ethers and esters such as ethanol, diethyl ether, Tetrahydrofuran, ethyl acetate and ethyl benzoate.

The apparatus used for the co-milling treatment is also not specifically specified, usually however, ball mills, vibration mills, rod mills or hammer mills are used. The conditions such as the pulverization or grinding temperature and the duration of the pulverization can be easily determined by the person skilled in the art determined by the pulverization method used. In alIqoinetnon the grinding temperature is in the Rorcich

BATH ORIGINAL

/ Ik

■ / Ik-

from 0 to 2OO ° C, preferably from 2O to 100 ° C, and the Milling times in the range from 0.5 to 50 hours, preferably 1 to 30 hours. The process of common Milling should of course be carried out under an inert gas atmosphere and the access of moisture should be suppressed if possible.

Particularly preferred for the purposes of the invention is a method according to which components (1) to (4) are reacted with one another in solution, or a method according to which components (1) to (3) are reacted in solution and the reaction product obtained is ground and reacted together with component (4).

The applicable quantitative ratio of components (1) and (2) is determined by the fact that both at one to small as well as too large an amount of the compound of the general formula Me (OR) X the tendency to

: ^ ρ z-p

stands / that the polymerization activity is reduced. To produce a highly active catalyst, it is desirable to use a range from 1: 0.001 to 1:20, preferably 1: 0.01 to 1: 1 and in particular 1: 0.05 to T-: 0.5, expressed as the molar ratio Mg / Me.

The applicable ratio of components (1) and (3) is such that the proportion of component (3) in the range from 0.1 to 300 g, preferably 0.5 to 200 g, per 100 g: of the component (1).

It is particularly preferred to adjust the amount of the halogen-containing titanium compound so that the amount of the in the solid catalyst component contained titanium in the range of 0.5 to 20% by weight. The range from 1 to

BATH ORIGINAL

10% by weight is particularly desirable in order to develop a well balanced activity based on titanium and / or vanadium as well as based on the solid.

In preparing the solid catalyst component, it is also preferable to use one as the ingredient (5) or more compounds from the group of organic halides, halogenating agents, phosphoric acid esters, Electron donors and polycyclic aromatic compounds, in addition to ingredients (1) to (4) to use. The reaction method in the case of using the component (5) is not particularly limited. A method is preferably used in which components (1) to (5) are in solution with one another are reacted, or a method according to which the components (T), (2), (3) and (5) are reacted in solution and the obtained reaction product with the component (4) is ground together.

When the component (5) is used, its amount is in the range of 0.01 to 5 mol, preferably 0.05 to 2 moles per mole of the ingredient (1).

Organic halides used as ingredient (5) are saturated or unsaturated aliphatic hydrocarbons and aromatic hydrocarbons, which are partially halogen-substituted. The halogen substituent can be selected from the group fluorine, Chlorine, bromine and iodine can be chosen.

Examples of such organic halides include methylene chloride, chloroform, carbon tetrachloride, bromochloromethane, Dichlorodifluoromethane, i-bromo-2-chloroethane, Chloroethane, 1,2-dibromo-1,1-dichloroethane, 1,1-dichlorothane,

1,2-dichloroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane,
Hexachloroethane, pentachloroethane, 1,1,1,2-tetrachloroethane, 1, 1,2,2-tetrachloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1-chloropropane, 2-chloropropane, 1, 2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1,1,1,2,2,3,3-heptachloropropane, 1,1,2,2,3,3-hexachloropropane, octachloropropane, 1, 1,2-trichloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane, 1,2-dichlorobutane, 1,3-dichlorobutane, 1,4-dichlorobutane, 2, 2-

Dichlorobutane, 1-chloropentane, 1-chlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, vinyl chloride,
1,1-dichloroethylene, 1,2-dichloroethylene, tetrachlorethylene, 3-chloro-1-propene, 1,3-dichloropropene, chloroprene, oleyl chloride, chlorobenzene, chloronaphthalene, benzyl chloride,

Benzylidene chloride, chloroethylbenzene, styrene dichloride and α-chlorocumene.

Examples of halogenating agents that can be used as ingredient (5) include non-metal halides such as sulfur chloride, PCI., PCI, - and SiCl ₄ , and
Non-metal oxyhalides such as POCl ₃ , COCl ₂ , NOCl ₂ , SQCl ₂ and SO ₂ Cl ₂ . "■" - ■, -

Examples of electron donors that can be used as ingredient (5) include alcohols, ethers, ketones, Aldehydes, organic acids, esters of organic acids, acid halides, acid amides, amines and nitriles.

Suitable alcohols are, for example, alcohols with 1 to 18 carbon atoms, such as methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol,

t \

BATH ORIGINAL

Stearyl alcohol, oleyl alcohol, benzyl alcohol, naphthyl alcohol, Phenol and cresol.

As ethers, for example, ethers with 2 to 20 carbon atoms can be used, such as dimethyl ether, Diethyl ether, dibutyl ether, isoamyl ether, anisole, phenetole, Diphenyl ether, phenyl allyl ether and benzofuran.

As ketones, for example, those with 3 to 18 carbon atoms can be used, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone, methyl phenyl ketone, ethyl phenyl ketone and diphenyl ketone.

Suitable aldehydes are, for example, those with 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, Octylaldehyde, benzaldehyde and naphthaldehyde,

Organic acids that can be used, for example, are those with 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Pivalic acid, caproic acid, caprylic acid, stearic acid, oxalic acid, malonic acid, succinic acid, adipic acid, Methacrylic acid, benzoic acid, toluic acid, anisic acid, oleic acid, linoleic acid and linolenic acid.

As esters of organic acids, for example, those with 2 to 30 carbon atoms can be used, such as methyl formate, methyl acetate, ethyl acetate, propyl acetate, Octyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Methyl methacrylate, methyl benzoate, ethyl benzoate, propyl benzoate, octyl benzoate, phenyl benzoate, benzyl benzoate, ethyl-O " melhoxyb <> n / .o. »l., Hu Iy 1 -p-cl hoxybc: M / .o.i I, M <· t liy 1 -p ~ t <> 1 i-iy 1 .ι t, Ethyl p-toluylate, ethyl p-ethylbenzoate, methyl salicylate, Phenyl salicylate, methyl naphthoate, ethyl naphthoate and ethyl

- SO-

anisate.

Suitable acid halides are, for example, those with 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, Toluoyl chloride and anisoyl chloride.

Acetamide, benzamide and toluamide, for example, are suitable as acid amides.

As amines, for example, methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, Aniline, pyridine, picoline and tetramethylenediamine can be used.

Examples of suitable nitriles are acetonitrile, benzonitrile and tolunitrile.

Phosphoric acid esters which can be used as component (5) are those represented by the general formula

OR

P-OR
0 OR

in which the radicals R can be the same or different and for hydrocarbon radicals' with 1 to 24 carbon * - atoms stand- Examples of such compounds include triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, Tribenzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritol! Phosphate, trixylyl phosphate and diphenyl xylenyl phosphate.

For examples of polycyclic aromatic compounds, which can be used as ingredient (5) include naphthalene, phenanthrene, triphenylene, chrysene, 3,4-benzophenanthrene, 1,2-Benzochrysen, Picen, Anthracen, Tetraphen,

al-

1,2,3,4-dibenzanthracene, pentaphene, 3,4-benzopentaphene, tetracene, 1,2-benzotetracene, hexaphene, heptaphene, diphenyl, fluorene, biphenylene, perylene, coronene, bisantene, ovals, pyrene, perinaphthene and their halogen - and - ¹ alkyl substitution derivatives.

The solid catalyst component thus obtained can on Oxides of metals of groups II to IV of the periodic table of the elements are applied and these The type of application is preferred. In this

In this case, not only the oxides of metals of groups II to IV of the periodic table can be used individually, but also double oxides of these metals and mixtures thereof. Examples of such metal oxides include MgO, CaO, ZnO, BaO, SiO ₃ , SnO ₃ , Al ₃ O ₃ , MgO-Al ₃ O ₃ , SiO ₃ -Al ₃ O ₃ , MgO-SiO ₂ , MgO-CaO-Al ₃ O ₃ and Al ₃ O ₃ -CaO, with SiO ₃ , Al ₃ O ₃ , SiO ₃ -Al ₂ O ₃ and MgO-Al ₃ O _{3 being} particularly preferred.

The method of applying the solid catalyst component on the oxide of a metal of groups II to IV of the periodic table of the elements is not subject to any special Restriction. As a preferred example, a method can be used according to which the components (1), (2), (3) and, if desired, also component (5) using an ether as a solvent in the presence of the Metal oxide are reacted with each other, after which the liquid phase by washing, drying or other suitable Methods is removed, whereupon the component (4) together with a hydrocarbon such as hexane, is added and reacted to prepare the supported solid catalyst component.

As organometallic compounds suitable according to the invention be organometallic compounds of metals from groups I to IV of Ferioclensyr. I called one dor Klomonic, dl ο as

Components of Ziegler catalysts are known, with organoaluminum compounds and organozinc compounds being especially preferred. Examples of such compounds include organoaluminum compounds of the general formulas R ₃ Al, R ₃ AlX, RAlX ₃ , R ₂ AlOR, RAl (OR) X and R ^ Al X-, in which the radicals R can be the same or different and represent alkyl , Aryl or aralkyl groups with 1 to 24 carbon atoms and X is a halogen atom, as well as organozinc compounds of the general formula R “Zn, in which the radicals R are identical or different and represent alkyl groups with 1 to 24 carbon atoms. Examples of such compounds are triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisecbutylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and diethylzinc. Organocarboxylic acid esters such as ethyl benzoate, ethyl o- or p-toluylate and ethyl p-anisate can be used together with these organometallic compounds. The amount of the organometallic compound to be used is not particularly limited. Normally, they may range from 0.1 to 1000 moles per mole of titanium compound and / or Vandinverbindung ^f respectively.

The olefin polymerization using the invention Catalyst can be in the form of suspension polymerization, solution polymerization or vapor phase polymerization be carried out, the vapor phase polymerization is particularly effective. The polymerization reaction is carried out in the same manner as the usual olefin polymerization reaction carried out using a Ziegler catalyst, i.e. under essentially oxygen and anhydrous conditions and, in the presence or absence, of an inert hydrocarbon. Suitable polymer

sationsbedingungen for olefins include temperatures in the range of 20 to 12O ⁰ C, preferably 50 to 1OO ° C, and pressures ranging from atmospheric pressure to 70 bar (kg / cm ^2), vorzugswese 2 to 60 bar (kg / cm ^2).

The adjustment of the molecular weight can be done to a certain extent Scope by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the addition of hydrogen to the polymerization system is for this purpose more effective.

With the aid of the catalyst according to the invention can of course Two or more stage polymerization reactions can also be carried out without difficulty, with in different polymerization conditions, such as different hydrogen concentrations, in the different stages and different polymerization temperatures can be used.

The inventive method is based on polymerization all olefins can be used that can be polymerized with a Ziegler catalyst, the polymerization of α-olefins with 2 to 12 carbon atoms in particular is preferred. For example, it is suitable for the homopolymerization of o-olefins such as ethylene, propylene, Butene-1, hexene-1, 4-methylpentene-1 and octene-1, the Copolymerization of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-i, Ethylene and octene-1 and propylene and butene-1, and the Copolymerization of ethylene and two or more other α-olefins.

In addition, the copolymerization of olefins with dienes can also be carried out in order to modify polyolefins.

Examples of dienes that can be used in this copolymerization include butadiene, hexadiene-1,4, Ethylidene norbornene and dicyclopentadiene.

The invention is illustrated by the following examples, without being restricted to them target.

example 1

(a) Preparation of a solid catalyst component

In a 500 ml three-necked flask fitted with a stirrer 200 ml of ethanol, 20 g of ethoxymagnesium chloride (Mg / Cl molar ratio = 0.81) were obtained by Treatment of magnesium diethoxide with HCl, 15g aluminum tri-see. -butoxide and 20 g of tetraethoxysilane given and the reaction was allowed to proceed under reflux of ethanol for 3 hours. Then the ethanol evaporated, after which 200 ml of hexane and 5 ml of titanium tetrachloride added and reacted for 2 hours under reflux of hexane. Then the supernatant liquid was removed, whereby a solid catalyst component was obtained, which was washed three times with hexane. It turned out that the solid catalyst component contained 25 mg of titanium per g.

(b) polymerization

A stainless steel autoclave was used as the vapor phase polymerizer used and a circuit was made with the help of a fan, a flow regulator and a dry cyclone. The temperature of the Autoclave was made by passing warm water through a

Coat set.

In the set at 8O ⁰ C autoclave, the above-prepared solid catalyst component and triethylaluminum at rates of 50 mg / hr and 5 mmoles / given h and then, were ethylene fed butene-1 and hydrogen in gaseous form, the proportions were set so that the molar ratio of 1-butene / ethylene in the vapor phase in the autoclave was 0.27 and the hydrogen concentration was 1.5% of the total pressure.

The polymerization was carried out while the gases inside the system were circulated with the aid of the blower and the total pressure was kept at 10 bar above atmospheric pressure (10 kg / cm ² above atmospheric pressure). The ethylene copolymer thus prepared had a bulk density of 0.28, a melt index (MI) of 1.2 and a density of 0.9203. The catalyst activity was 254,000 g copolymer / g Ti.

After continuous operation for 10 hours the autoclave opened and its inside checked. It was found that the inner wall of the autoclave and the Stirrers were clean and free of adhering polymer.

The FR value (FR = MI ₁ ./MI..,), Which is the ratio of the melt index MI _{1 of} the copolymer, determined under a load of 10 kg, to the melting index MI_ .. ,, determined under a load of 2, 16 kg is expressed, both measurements being carried out at 190 ⁰ C according to the method according to ASTM-D1238-65T, was 7.2. The molecular weight distribution of the copolymer was thus very narrow.

A film was formed from the copolymer and extracted in boiling hexane for 10 hours. It was found that the hexane extract was 1.3% by weight, which is very little.

- 22 "-

Comparative example 1

A solid catalyst component was prepared in the same manner as in Example 1 except that no tetraethoxysilane was added. This component contained 21 mg titanium per g.

The continuous vapor phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 carried out with the modification that the solid catalyst component prepared above at a rate of 50 mg / h was added. The ethylene copolymer thus prepared had a bulk density of 0.25, a density of 0.9213 and a melt index of 1.2. The catalyst activity was 186,000 g copolymer / g Ti.

The F.R. value of the copolymer was 8.2. A slide was prepared from the copolymer and extracted in boiling hexane for 10 hours. It turned out that you Hexane extract was 4.2% by weight.

Example 2

\ ϊ ■ \ (a) Production of a solid catalyst component

A solid catalyst component was prepared in the same manner as in Example 1 except that 15g boron triethoxide instead of 15g aluminum tri-see-butoxide were used. It contained 27 mg titanium per g.

ORIGINAL

(b) polymerization

The continuous vapor phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that that prepared above solid catalyst component was fed in at a rate of 50 mg / h. The ethylene copolymer thus produced had a bulk density of 0.27, a density of 0.9195 and a melt index of 1.1. The catalyst activity was 223,000 g copolymer / g Ti and was therefore very high.

After operating continuously for 10 hours, the autoclave was opened and its inside was checked. Included It was found that the inner wall of the autoclave and the stirrer were clean and free of adhering polymer.

The F.R. value of the copolymer was 7.3. A slide was prepared from the copolymer and extracted in boiling hexane for 10 hours. It was found that their hexane extract was 1.5% by weight and was therefore very low.

Example 3

(a) Preparation of a solid catalyst component

A solid catalyst component was made in the same manner prepared as in Example 1, with the modification that 20 g of a pentamer of tetraethoxysilane were used in place of 20 g of tetraethoxysilane. It contained 21 mg Titanium per g. '

BATH ORIGINAL

... ·: ■ '.: ·.: .. 3 2 AA 8 71

a * -

(b) polymerization

The continuous vapor phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 carried out, with the modification that the above just prepared solid catalyst component in one Rate of 50 mg / h was supplied. The ethylene copolymer produced in this way had a bulk density of 0.34, a density of 0.9200 and a melt index of 1.0. The catalyst activity was 332,000 g copolymer / g Ti and was therefore very high.

After operating continuously for 10 hours, the autoclave was opened and its inside was checked. Included It was found that the inner wall of the autoclave and the stirrer were clean and free of adhering polymer.

The F.R. value of the copolymer was 7.2. A slide was prepared from the copolymer and extracted in boiling hexane for 10 hours. It was found that its hexane extract was 1.3% by weight and was thus very small.

Example 4

(a) Preparation of a solid catalyst component

In a 500 ml three-necked flask equipped with a stirrer were 2OO ml of n-hexane, 20 g of n-buty! magnesium chloride, 15 g Aluminum triethoxide and 20 g of triethoxymonochlorosilane were added and the reaction was carried out under reflux of hexane for 3 hours. After that, the supernatant liquid became removed and the reaction product was dried to obtain a white solid substance.

BAD'ORIGINAL

Thereafter, there was 10 g of the solid substance thus prepared and 1.2g titanium tetrachloride in a stainless steel vessel Steel with a capacity of 400 ml, the 25 stainless steel balls with a diameter of each 1.27 cm and ball milling was carried out for 16 hours at room temperature under a nitrogen atmosphere carried out to obtain a solid catalyst component containing 27 mg of titanium per g.

(b) polymerization

The continuous vapor phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that those as above produced solid catalyst component was fed at a rate of 50 mg / h. The ethylene copolymer thus produced had a bulk density of 0.31 density of 0.9205 and a melt index of 1.1. The catalyst activity was 258,000, g copolymer / g Ti and was thus very high.

After continuous operation for 10 hours the autoclave opened and its inside checked. It was found that the inner wall of the autoclave and the Stirrers were clean and free of adhering polymer.

The F.R. value of the copolymer was 7.5. A slide was made made from the copolymer and extracted in boiling hexane for 10 hours. It turned out that you Hexane extract was 1.4% by weight and was therefore very small.

BAD ORiQlNAL

-3Ο ·

Example 5

A 2-liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and then charged with 1000 ml of hexane, after which 1 mmol of triethylaluminum and 20 mg of the solid powder obtained in Example 1 were added and the temperature was raised to 90 ° C. with stirring . Due to the vapor pressure of hexane, the system was under a pressure of 2 bar above atmospheric pressure (kg / cm ² above atmospheric pressure). Hydrogen was then passed in until the total pressure was 4.8 bar above atmospheric pressure and finally ethylene was passed in such that the total pressure was maintained at 10 bar above atmospheric pressure. The polymerization was carried out for 1 hour. Thereafter, the polymer slurry was transferred to a beaker and the hexane was removed under reduced pressure to obtain 183 g of a white polyethylene having a melt index of 1.3 and a bulk density of 0.33. The catalyst activity was 70,400 g polyethylene / g Ti.h.

C "H, pressure or 1760 g polymer / g _{solids.hC 3} H ₄ pressure.

The F.R. value of the polyethylene was 8.2; the molecular weight distribution was therefore very narrow. The hexane extract of the polymer was 0.15% by weight, which is very low.

Claims (1)

STREHL ^: sajuBi4, -PK) PF ■ ^ (- MiULZ 324 A871 WIDICNMAYKKSTKASSIC 17. I) H (K) O MÜNCIIKN 22. I) Il ¹ I .. IN «.. I'M KU STKWil. · I) IIM .. CIIHM. I) U. URSULA SCHIIIIKI. IIOI'K ' I) II ¹ I ..- J'HYS. IJK. K (JTUICK SCHUL / ^1. · ALSO LAWYER DII'L. ING. KEINHARD WEISK • SO EUROPEAN PATENT ATTORNEY TELEPHONE (OKS)] 22 3911 TELEX 5 21 403G SSSM I) TELECOPIER (0H9) 223915 DEA-13 732 December 3, 198 2 PATENT CLAIMS 1. Process for the preparation of polyolefins by polymerizing at least one olefin in the presence of one Catalyst, which is formed from a solid catalyst component and an organometallic compound, thereby g e characterizes, that it has as a solid catalyst component a substance which by reaction at least of the following four ingredients is available: (1) a compound of the universal form] (2) a compound of the general formula Me (0R ³ ) _p X _z _ _p , (3) a compound of the general formula ß I ₇ R -t ~ Si - 0 -} - R
^q (4) a halogen-containing titanium compound 01 • Ä · 12 3 7 where in the formulas R, R, R and R each one Hydrocarbon radical with 1 to 24 carbon atoms, 4 5 6
R, R and R each have a hydrocarbon radical 1 to 24 carbon atoms, an alkoxy group Hydrogen atom or a halogen atom, X a halogen atom, Me is an element from groups I to VIII of the Periodic Table of the Elements, with the exception of silicon and titanium, ζ is the valence of Me and m, η, ρ and q in the following There are correlations: 0 = m = 2, 0 = n <2, .10 0 <m + n = 2, 0 <ρ = z, 1 = q = 30. 2. The method according to claim 1, characterized in that the components (1) and (2) in a ratio in the range from 1: 0.001 to 1: 2O in terms of Mg / Me molar ratio will. 3. The method according to claim 1 or 2, characterized in that the components (1) and (3) in such a ratio that the proportion of the component (3) in the range of 0.1 to 300 g per 100 g of component (1) is. 4. The method according to any one of claims 1 to 3, characterized characterized in that the component (4) is based in an amount in the range from 0.5 to 20% by weight to the titanium contained in the solid catalyst component. 5. The method according to any one of claims 1 to 4, characterized in that Me for Na, Mg, Ca, Zn, Al, B, P or Fe stands. 6. The method according to any one of claims 1 to 5, characterized in that the halogen-containing Titanium compound a titanium halide or a titanium alkoxy 02 halide is. 7. The method according to any one of claims 1 to 6, characterized in that the solid Catalyst component is a substance that by reacting the ingredients (1) to (4) with a ι
further constituent (5) is obtained which represents at least one compound from the group of organic halides, halogenating agents, phosphoric esters, electron donors and polycyclic aromatic compounds. 8. The method according to claim 7, characterized in that the component (5) in one Amount of 0.01 to 5 moles per mole of the component (1) is used. 9. The method according to any one of claims 1 to 8, characterized characterized in that the solid catalyst component is based on an oxide of a metal from groups II to IV of the periodic table is plotted. 10. The method according to any one of claims 1 to 9, characterized characterized that as an organometal! compound an organoaluminum compound or an organozinc compound is present. 11. The method according to any one of claims 1 to 10, characterized in that the polymerization reaction is carried out at a temperature in the range from 20 to 120 ° C and under a pressure in the range from atmospheric pressure to 70 bar (kg / cm ² ). 12. The method according to any one of claims 1 to 11, characterized characterized in that the olefin is an α-olefin is polymerized with 2 to 12 carbon atoms. 03 ::. · - · "■ C- . '. 32U871 • if ·. 13. KaLalytjatorkomponente for the production of polyolefins according to one of claims 1 to 12, characterized in that it represents a substance by implementing at least the following four components (1) a compound of the general formula R (OR) MgX _? _ _, (2) a compound of the general formula (3) a compound of the general formula R ⁴ 6 I ₇ R - t - Si - O -> - R I ^q '' 5 and (4) a halogen-containing titanium compound where in the formulas R, R, R and R each a hydrocarbon radical with 1 to 24 carbon atoms, 4 5 6
R, R and R each represent a hydrocarbon radical with 1 to 24 carbon atoms, an alkoxy group, a Wii!; R; ers1.of fni.orn odor ojn Hai ocjcnnlom, X a Hai ogonalom, Me an element of groups 1 to VIII of the periodic table of the Elements, with the exception of silicon and titanium, mean that ζ is the valence of Me and m, η, ρ and q are in the following relationships: 0 = m = 2, 0 = n <2, 0 <m + n = 2, 0 < p = z, 1 = q = 30 _T and optionally a constituent (5) which is at least one compound from the group consisting of organic halides, halogenating agents, phosphoric esters, electron donors and polycyclic aromatic compounds is obtainable.