DE2003075A1 - Process for producing an olefin polymer - Google Patents

Description

The present invention relates to the polymerization of olefins with the aid of catalysts such as are known uhtej by the name Ziegler catalysts ₍ and it relates both to the polymerization of olefins and the resulting polyolefins, including copolymers, and to the production of Ziegler catalysts which are used. are suitable in the polymerization of olefins, and the resulting catalysts. - <.

A Ziegler catalyst can be prepared by for example a compound in an olefin polymerization vessel a transition metal in which the transition metal is in

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009831/1749

BATH ORIGINAL

a bond state that is below its normal maximum, e.g. brings together titanium trichloride and an organometallic compound such as aluminum diethyl monochloride _f , which essentially serves as an activator for the transition metal compound but also to intercept the catalyst-deactivating impurities that come into the polymerization vessel are. Such a Ziegler catalyst can also be formed outside the polymerization vessel and added to it, optionally with additional organometallic compound, but the formation inside the polymerization vessel in the specified manner is a

fc favorable practice for practice. The transition metal compound! which is found in a binding state below the normal maximum, is usually reduced by reducing the corresponding Obtain compound that contains the metal in its normal maximum binding state. Titanium trichloride e.g. is normally produced by the reduction of titanium tetrachloride made with aluminum alkyl or alkyl halide as reducing agent. This reduction step can be carried out simultaneously with the formation of the catalyst, using the same aluminum alkyl as both reducing agent and is used as a catalyst activator ·, the titanium trichloride used to form the catalyst is so in situ

^ manufactured. It is now generally preferred, however, carry out the reduction of the transition metal as an independent step and then the organometallic compound to the to add the reduced compound thus formed, either inside or outside the polymerization vessel.

Normally the polymerization is carried out in a reaction medium such as an inert organic liquid, for example an aliphatic hydrocarbon ₍ and the catalyst and one or more olefins are contacted in some suitable manner. A molecular weight regulator

BATH ORIGINAL

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which is normally hydrogen is generally that .Reaction vessel present to prevent the formation of undesirably high molecular weight To suppress polymers. Many forms of Ziegler catalysts are known and as are also known is, can, many transition metal compounds and organometallic compounds Compounds for the formation of Ziegler catalysts can be used. Such catalysts can also do more as a transitional field connection together with an or contain several organometallic compounds and / or such catalysts may contain additional compounds * - hold that has a modifying effect on the nature of the. Catalyst and / or have on the course of the polymerization.

For obvious economic reasons, it is desirable that the. Ziegler catalyst has a high catalytic effect during the polymerization, and a solution to the problem of improving the catalytic effect has been achieved either by attempting to increase the catalytic effect of the catalyst itself or by changing the polymerization conditions change, e.g. increase the pressure, in order to achieve the maximum rate of polymerization per unit of the usual catalysts which the practical conditions allow or a combination of these means. However, other considerations are also important, for example, market requirements determine the type of polymer to be made and this may determine the type of catalyst and / or polymerization conditions that can be used. It also determines the level of catalyst-forming residues in the polymer Degrade polymer product without resorting ■ to complicated and expensive cleaning steps. -.- "'"...-''. - ■ _ ■ "■■ - ^: -

.As stated above, the transition metal compound is the ■ rsieh ■ is in a -. valence levely '· the one below -your "- ■" - ■ -: ■ normal maximum, usually by reducing the corresponding connection that the metal in its

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.. , ., BATH

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contains normal valence level. For the sake of convenience, this reduction is normally carried out using an organometallic compound as the reducing agent which contains the same metal, advantageously aluminum, as is used as the activator for the Ziegler catalyst. However, it is also possible to carry out the reduction step by using a different organometallic compound than is used to activate the Ziegler catalyst formed. For example, titanium tetrachloride can be reduced with an organic magnesium compound and activated with an organic aluminum compound. It has now been found P that can be achieved with use of organic magnesium compounds as the reducing agent advantageous results when carrying out the reduction at a temperature below ⁰ ° C. When operating at these reduced temperatures, two main advantages can be achieved. 1. the activity of the resulting polymerization catalyst is increased and 2. the bulk density of the polymer product ultimately formed is increased. Accordingly, the present invention provides a process for producing an olefin polymer before, are brought together in which the olefin monomer with a catalyst which has been prepared by reacting a transition metal compound in * its normal maximum Y / ertigkeitsstufe below ⁰ C ^f with an organomagnesium Compound reduces uhd the reduction product activated in that it is with a Trihydroculylaluminiuiaverbinduns d _t h. of an aluminum compound with 3 hydrocarbon radicals as an activator * It is assumed that in the reduction process, which is carried out under the regulated conditions described here, the magnesium atoms are converted into the solid phase of the reduced superfluous compound in a particularly effective manner .g and that the presence of this / 'tone in the resulting activated Ziegler catalyst is one of the reasons for the increased activity of the catalyst according to this V.vZ In-

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Any transition metal compound (or mixtures thereof) formed by a Organomagnesium compound can be reduced from its normal maximum valency level, and in which the Connection with a lower valence in the presence of a organometallic activator can act as an olefin polymerization catalyst, can when carrying out the Procedure can be used, It .. can, likewise, any an./organometallic compound known to be for the activation of ZiegleroLef ^ polymerization catalysts suitable to be used for activating the reduced transition metal compound. Such suitable transition metal compounds include titanium, vanadium, chrome? Molybdenum and Zirconium halides and suitable organometallic compounds include aluminum}. Zinc and magnesium alkyls and alkyl halides. However, as is well known, the most suitable Ziegler catalysts are those obtained by reduction of titanium tetrachloride and activation of the resulting trichloride obtained with ein.Aluminiumalkyl or RajLkylhalogenid will. Accordingly, the present invention will hereinafter be described with particular reference to this type of catalyst system described, although it is obvious. .that · it is not limited to such a system, but generally to the production of all types of Zieglerkatalysato-. ren is applicable. ·. - ν

Many types of organomagnesium compounds of the present invention are used as a reducing agent ACCORDANCE, but for reasons of convenience, it is mm preferred generally to use compounds of the type, "such as employed in the reaction between a Organohalpgenid of _v. Formula RX (in R is a hydrocarbon group and X is - _; - _; halogen atom) and magnesium metal is formed. The term "Grignard reagent" is often used to denote compounds ·;. »..,: -. of this type and the For the sake of simplicity, this -; ,, term is used frequently in the present invention., ^: _V -.--

• "■:; ^ä '■ - ■ · -6-

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It should be noted, however, that _| although the term "Grignard reagent" is sometimes used in a narrow sense to denote the ether rates of the organomagnesium halides which are formed when the above reaction is carried out in ether as a solvent, the term is used here in its broadest sense to mean any To designate the type of organomagnesium compound which is formed in the above general reaction. The term "Grignard reagent" as used here encompasses not only the hydrocarbyl • magnesium halides of the formula R Mg X (possibly dissolved) but also the dihydrocarbyl magnesium compounds of the formula RpMg, as well as the forms of the two types of compounds which can be obtained when the G-rignard reaction is carried out in an inert (ie non-solvent) solvent such as a hydrocarbon. .

Although any type of Gridnard reagent can be used for the process according to the invention, it has been shown that the etherates which arise when magnesium and e-in hydrocarbon halide are allowed to react in the presence of an ether _(show the advantageous results of this process to a lesser extent . Accordingly, it is preferable in the present method, the kind of Grignard reagents to be used which is obtained by the reaction of a hydrocarbyl halide of the formula RX with magnesium metal in the absence of the ether. it is assumed that ^r deratige ether free Grignard reagents are often present in associated form. For reasons of economy, it is preferred to use those compounds in which X is a chlorine or bromine atom, while the optimum activity of the activated catalyst is generally achieved using a Grignard compound in which R is an alkyl group of at least 4 and conveniently at least s 8, special; ·. VA is carbon atoms. The Grignard compounds with higher alkyl.

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Groups, however, require some reagents to make them, and so the choice of one ultimately depends suitable alkyl. for the Grignard compound in general on calculating the economic factors of convenience and effectiveness.

Grignard compounds are well known from the chemical literature .in. of which many methods are given for their manufacture. To produce the kind of alkylmagnesium halides are preferred for the present invention, is a convenient method described by Bryce Smith in Chem. & Ind. (I960) I533, ^^ ^ll 3feSi ^b iagnesiummetall and the alkyl halide in a hydrocarbon in the presence of a Alcohol advantageously 1 mol $ ethanol can be heated as a catalyst. Another suitable manufacturing process is that of Zakharkin, Okhlobystin and Strunin in Tetrahedron Letters. (1962) 631, by which many different Grignard compounds can be obtained by heating magnesium and alkyl halide in iso-oetane as solvents. These stocks generally result _in a slurry which contains the desired Grignard reducing agent partly in the liquid phase and partly as an undissolved solid material. The entire reaction product slurry may be used as a reducing agent for the process of the invention, but the presence of the insoluble components may lead to difficulties and it is therefore often preferable the Grignard reagent as a soluble ^r rödukt off

- e
to separate. The most convenient way of achieving this is to extract the organomagnesium reaction product with a suitable solvent which can either be added after the reaction between magnesium and hydrocarbon halide or at least partially be present during the reaction. In any case, are ^one usually at least two portions of the solvent ^ erföräerliefo a sufficiently complete extraction ZM erzieüai *

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Thus, a preferred method for preparing the Grignard reagent is _r that magnesium metal and a -Kohlenwasserstoffhalogenid optionally in the presence of a solvent such as iso-octane or toluene and, where gene if catalytic in the presence of amounts of alcohol together react läßtjund the desired Grignardreagene extracted by reacting the mixture with a heated under reflux suitable solvent and the resulting solution is separated off. Where in this specification the term "Grignard reagent" is used, it is intended to refer to the product which is produced by the reaction of magnesium metal and a hydrocarbon

fc halide is formed regardless of whether the product P or

in the form of the reaction sludge is used, whether it is through Solvent extraction removed from the insoluble products

Before
separates / is. Where the latter type of product is meant, the term "Grignard's solution" is used specifically.

This reagent can be combined with the titanium tetrachloride in any of the known ways for the reduction of this compound to titanium trichloride Wise implemented, however, it has proven particularly easy to use the Grignard reagent with titanium tetrachloride to implement, which is dissolved in the same hydrocarbon solvent that is used to prepare the Grignard reagent fe has been used. These reactants can be in any can be put together in any order, it has become

höhc-cs

however, shown that better results, such as will receive a / bulk density often when applying ¹ 'method, a so-called "reverse additives, wherein the titanium tetrachloride to the reducing agent - inpiesem case is added to the Grignard reagent, and therefore this order is preferably The concentration of the Grignard reagent in the reducing sludge, the concentration of the titanium tetrachloride solution used and the relative proportions of these two reactants can be varied within wide limits in order to achieve particularly favorable reaction conditions.

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The temperature at which the Grignite reduction lamb and titanium tetrachloride react together is important as it affects the physical form and activity of the resulting catalyst, as well as the physical properties of the polymer product, as noted above The property of the present invention is characterized by the fact that the reduction is carried out at a temperature below OG, since this leads to higher catalyst activities and higher bulk densities of the polymer product are prepared, it is found that leads a decrease in temperature from room temperature to 0 C in a decrease in catalyst activity, but that increases surprisingly, further decreasing temperature the catalyst activity greatly and is significantly greater than that achieved with a reduction in room temperature will. A significant increase in catalyst activity to achieve., The temperature should be substantially below 0 G and be cheaper at most -30 C, and particularly not exceed -60 C .. Another significant. Advantage when using reduction temperatures below von.O ⁰ C according to the present invention ',. , consists in ... that a higher bulk density of the polymer product is achieved. In relation to these _equity: Community h.at it shown yourself that vsie of.. Catalyst temperature, duct temperature, is inversely proportional, and that. so e, ine continuous. Increase in bulk polymer weight:; ·

^ y,: if the reduction temperature is lowered from, .Zimmer-! ··: temper.atyr / -60 ° G ⁷ . So. is- it. ,, although · «es, ^ ₁ -i ^ sometimes _: rr.ö _; equal, is, by reduction at room temperature>-; ..,. · ■ ·.;.; temperature to achieve catalyst activities that; .with the-.:iLJ jenäge-n, are comparable to that at reduction temperatures ';' below 0 U can be achieved, especially if -the>? ■ - "·

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Reduction temperature is not far below OC '. J normally not possible to achieve high catalyst activity and high bulk density together using the The catalyst reaction is not carried out below 0.degree.

The rate at which the titanium tetrachloride is added should of course be set so that the heat developed can be dissipated without the reaction temperature increasing beyond the permitted limits. After this addition, the mixture is allowed to warm to room temperature and is then conveniently left to stand for more than eight hours in order to achieve a complete reaction process, during which time stirring is carried out. The Titantriehloridschlamm may then optionally be heated for a time to achieve, for example, for 6 hours at 8O ⁰ C for an optimal activity.

The titanium trichloride produced by Grignard reduction can then use any of the methods used to manufacture Ziegler catalysts

en
known type / used. So the Grignard reduction

product can be used as such or "it can first be washed free of any unreacted titanium tetrachloride and other soluble compounds, advantageously by decanting and reslurrying, this latter method being preferred. Likewise, the titanium trichloride is advantageously _χ but not necessarily in the form of the" the sludge obtained in the reduction step, and not separated before use. In either case, the trichloride can be mixed with alkyl aluminum activator and then added to the polymerization vessel, or the trichloride and aluminum activator can be added separately to the polymerization vessel common activators that are used for the production of Ziegler catalysts,

* "use ■■■■. · ■■ .. ■». ■

has been activated./ However, it has been shown that the

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Use of aluminum dialkyl halides as activators leads to the formation of polymers that are unsuitable have a low melt index and accordingly exist an essential feature of the present invention is that -that the activator of the combined with the Grignard reduction product is a triorganoaluminum compound, • especially .trialkylaluminum. In addition, it has been shown that in-many fall aluminum trialkyls with long.

Carbon chains result in a more active catalyst than the usual triethylaluminum and therefore are preferred Activators aluminum trialkyls in which any alkyl chain more than 4 favorably at least 8 and especially. favorably contains no fewer than 11 carbon atoms, although the carbon chains should not be excessively long, as this leads to a reduction in activity. Triundecylaluminium 'is particularly suitable as an activator.

The relative ratio of titanium trichloride to aluminum alkyl can be set within the usual limits, e.g. in molar ratios from 1: 1 to 1:20, with catalysts arise that are suitable for certain Polymerisatiönsbedingungen are, but generally will be more active catalysts obtained when using molar ratios of 5: 1 to 10: 1 of activator to titanium trichloride. In accordance the Aikylalüminiuifl preferably in a suitable hydrocarbon solution * means used, which is favorably the same, dös in which Titätttrichloridschlamm is contained * Hexan und Isö * - octane are examples of technically and economically favorable solvents. ■

The particular polymerization process can be used accordingly any process shall be carried out, as it is with a The usual polymerisation process is used.

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In general, the catalyst or catalyst components placed in a hydrocarbon solvent in a polymerization vessel, in which then the olefin monomer or the monomers, if a copolymer is to be produced, are introduced and, advantageously, hydrogen as a regulator of molecular weight. The polymerization reaction can be carried out under any suitable pressure although at atmospheric pressure the yields are lower while the cost of the equipment becomes high when very high prints are used. Accordingly, it is preferred to carry out the polymerization with the catalyst according to the invention to be carried out at a pressure which is above atmospheric pressure, favorably below 100 atmospheres and suitably sometimes at about 3> 5 to 14 atm.

The present invention is particularly suitable for ethylene polymerization or copolymerization, but it can can also be applied to the copolymerization of ethylene with other 1-olefin monomers, which with the help of a Ziegler catalyst can polymerize, such as propylene. The present invention therefore relates, inter alia, to a catalyst which is used for olefin polymerisation is suitable, and a method for making such catalysts.

The invention is illustrated in more detail by the following example.

Example

The experiments described in this example show the increase in the catalyst activity and the polymer bulk weight, which is achieved by reducing the titanium tetrachloride at temperatures below ⁰ ° C., as well as the effect of the variables, the order of combining and the carbon chain length, in the trialkylaluminum activator.

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In order to make the comparison easier, values are also given for similar experiments in which reduction temperatures of O C and above were used. ·

Manufacture of the Grignard reagent

Three slightly different procedures were used, to obtain solutions of Grignard reagent used for the titanium tetrachloride reduction step. These are under the headings "Procedure A" "Procedure B" and ■ "Method G". ■ '· ...

Procedure A

0.55 mol of magnesium powder is placed in a dried 500 ml round-bottom flask which has been flushed with nitrogen and is provided with a stirrer, reflux condenser and dropping funnel. The magnesium is dried by, a long and two hours heating at 110 ⁰ C -.13-0, wherein a stream of nitrogen is passed continuously through the flask. After cooling to 50 - 60 ⁰ C 0.05 mole of Alkylhal-ogeni & s are about zufgegeben to the magnesium, and the flask in einem.Ölbad heated until the reaction begins. This is usually shown by the appearance of white fumes in the flask. ' The alkyl halide required up to a total of 0.5 mole is now slowly added through a dropping funnel at such a rate that the contents of the flask are kept at approximately the temperature at which the reaction began. This temperature depends on the alkyl halide used. In some cases it is necessary to additionally warm up with the help of an oil bath, in other cases the temperature is maintained by the exothermic reaction itself. It is difficult to stir at the beginning, but the "cake" formed first gradually turns into a "slurry" that can be stirred.

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After all Alkylhalog _e is nid added Stuhden is heated an additional 1 to the second Now the solvent, either a commercially available aliphatic hydrocarbon solvent], with a boiling range from 90 to 100 ° C. (SBPA) or toluene, is added and the mixture is refluxed for 2 to 3 hours. The volume of the solvent depends largely on the viscosity of the sludge obtained. Typically 2 - 300 ml are added first. The slurry is now allowed to cool and settle. This results in two or often 3 layers, an upper almost clear solution, a medium gray healing, mud-like layer and a lower dark gray layer hauptsäch- ψ lent besteht.Wegen of unreacted magnesium their high viscosity is difficult filtration of these solutions. The upper layer is decanted off under nitrogen pressure in a filter coated with a filter aid based on kieselguhr and filtered under a slight nitrogen pressure. The material remaining in the flask is refluxed with a further volume of the solvent, allowed to settle and decanted back into the filter It is often necessary to heat the filter with an IR lamp in order to achieve favorable filtration rates.According to the usual precautionary measures, the alkyl solution is protected with nitrogen in all stages.

Procedure B

This procedure differs only slightly from the procedure Λ, namely in, egg ate the alkyl halide in the form a solution in toluene or oBPA is added. That is favorable when the reaction is relatively violent, since the heat can be dissipated by the fact that the solvent is present Reflux boils. Otherwise, according to the procedure

Λ worked. _1r

- ι j

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Procedure C

This method can be used when the alkyl halide has a low reactivity and the reaction is difficult to get started. - To the dried magnesium powder and a small amount of the necessary alkyl halide in the reaction flask, 5 MoT / c isopropanol, based on the total alkyl halide, are added: When heated, the reaction starts steadily without a violent exothermic reaction occurring and the remaining alkyl halide can be added as a solution. The work-up is carried out as described above. In some cases this method gives slightly less viscous solutions.

Reduction of titanium tetrachloride

The catalysts were in a 250 ml glass reaction vessel manufactured. This consists of a cylindrical vessel with a flat bottom (FV250 Quickfit and Quartz), with a diameter of 50 mm and a length of 130 mm and a flat top edge. There are up to one on the walls Height of 70 mm from the floor and at an angle of 90 to each other four vertical indentations, which when stirring deflect the contents of the flask. A stirrer made of corrosion-free Steel with 4 blades and a diameter of 35 mm is attached to the central section of the reactor cover, wobd a double (iaco-ÖMichtaing is used to beating to diminish. In a second cut is a dropping funnel attached with an extended drip pipe and in other cuts in the chamber lid are a thermometer and a nitrogen inlet.

30 ml of the, alkyl magnesium halide solution are added together with sufficient additional solvent in the reaction vessel pipetted so that a volume of at least 75 ml is created.

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The solution is stirred at 600 to 650 rpm, cooled to the required temperature and 15 ml of TiCl . are slowly added as a 1m. solution in SBPA over 20 to 30 minutes. When the addition is complete, the cooling bath is removed and the slurry is allowed to warm to room temperature and stir for a further 8 hours at room temperature. The procedure described is a "reverse" addition. by "direct" (forward) addition is meant that the TiCl.solution is in the reaction vessel and the alkyl solution is slowly added. The TiCl ^ concentration of the slurry is determined by a method that the Oxyda-

W tion of the Ti in acidic solution due to excess iron -111-

2+ "ammonium sulfate and the determination of the Fe formed by titration with cerium sulfate. In cases in which not all of the TiCl _{4 has been} reduced, the unreacted is washed out by decanting the catalyst 4 or 5 times and reslurrying the catalyst in fresh SBPA.

Polymerization

3 1 SBPA were placed in a 5 1 reaction vessel equipped with a stirrer was verr-around, and heated to 8O ⁰ C. 3.0 mol of trialkylaluminum was added to the P reaction vessel as a 1 molar solution in SBPA, followed by 0.3 mmol of titanium trichloride, which had been prepared as described above. A 50:50 mixture of ethylene and hydrogen was passed through the SBPA solution for 3 hours at a rate of -200 pounds per hour at atmospheric pressure with stirring. After this time, 100 ml of sec-butanol were added to stop the polymerization. The polymer sludge was washed with hydrochloric acid and water, and the SBPA was removed by steam deposition. The polymer was dried and weighed and its melt flow properties determined.

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The experimental procedure described above became several Times using different temperatures for the titanium reduction step and different Trialkylaluminum activators and the results obtained are given in Table 1 below. The melt index in this table was based on B.S. 2782 method A measured and the flow parameter is defined as follows:,

¹ 21.6 kg.

FP = log_ _1A * i = melt index

" ¹⁰ 2 * 16 kg

• 2

The polymer bulk density is given in g / cm.

-following table-

BATH ORIGINAL

009831/1749

Table 1

Preparation of the catalyst Properties of the resulting polymer ^ ί
Ti 'Tempera
tur ⁰ C r additions
procedure Co-catalysis
satcr Medium specifi
cal polymerisa
tion s speed
^{speed g} C ₂ H ₄ / ^g cat- ^h
• Print 2
Pressure in kg / cm (ps: Enamel
index
-a) rs polymer
pour
weight 1
r Reducing
Alkyl and her
position adjustment
travel
C ₁₂ H ₂₅ MgBr (A) +25 "vice versa" ^{Al (C} il ^H 25 ⁾ 5
AI (C ₈ H ₁₇ ) ₅
Al (iC ₄ H ₉ ) ₅
A1 (C ₂ H ₅ ) ₃ 2141 (150)
1642 (115)
1742 (122)
485 (34) 1.0
2.4
2.2.
2.4 Flow
parame
ter 0.18
0.16
O.I7
0.15 C ₁₂ H ₂₅ Mg Br (A) +25 "direct" Al (C ₁₁ H ₂₅ ) J.
Al (C ₈ H ₁₇ ) ^
Al (iC _2L H ₉ ) ₅
A1 (C ₂ H ₅ ) ₃ 1958 (137)
2021 (143)
1529 (107)
572 (40) 1.8
4.4
4.2
5.0 I.72
I.65
I.67
I.69 0.18
0.16
0.18
0.11 • C ₁₂ H ₂₅ MgBr (A) 0 "vice versa" ^Α1 (- ° 1 · 1 ^Η 25> 5 1585 (111) 1.8 I.67
I.6O
I.65
.I.72 0.145 " I.
Previous year
VJ C- ₂ H _2K ; ig2r (A) -50 "vice versa" ^Α1 (° 11 ^Η 2 ^ 3014 (211) 5.4. 1.66 O.I7 S. ^W 12 2 ~ '* ° ^' -30 '■ "reversed" ai (c _{i; l} h ₂₅ ) ₃
A1 (C ₈ H ₁₇ ) ₅
AKi-C ₄ H ₉ ) ^
Al (C ₂ H ₅ ) ^ 2457 (172)
2372 (166)
2428 (170)
1171 (82) 6.6
6.1
5.2 *
2.5 I.65 Ο.25
Ο.27
Ο.25
0.19 O
33
δ
>
j "direct" Al (C ₁₁ H ₂ J) ₅ 1 2086 (146) 3.0 I.65
1.59
I.67
I.78 0.14 I.60

6 ^ 7 pounds. L / t ε 8 60 0

Tabel'. 1 (continued) "

Preparation of the catalyst,.; ·; .Z .: Properties of the resulting 'Tempera-;
door " ^Q C, Additions ^
procedure _; ■ So- ^ Ka t al y-
;: <"s'k ± ^: or ' ^: Medium -speciii ^
.see Polymerisa-
• tionssesG-hvvindig-
^ability ^ C ₂ I _A /% at * ^h
* Press ■ ο. '
Press in ..kg / cm (ps loin '^ olymer'S' ^, ν ^; ' pafäme-
... • t he "..", I pour
E-eVvicht
¹ '■■ ί
■ ■ ■ *. *. · ■ '.- Seductive _; ;
filkvl 'ürui Her'- I
■ steTlunfrsv ^ T- · ^Λ
!travel;. . ■ ■ ' -50; ' "vice versa ' ¹
»Directly» '■. ■ ai (c _{i: l} h ₂₃ ) ₃
A1 (C _U H ₂₅ ) ₅ 2Q5 2 (1.44)
.3114 (218) Enamel
index
la). . 1.85
1.70 0.52
0.20. ; C ₁₂ H ₂₅ MgBr (C) -60 "vice versa" Al (C ₁₁ H ^) ₃
¹ Al (C ₈ H ₁₇ ) ,,.
AId-C ₄ H ₉ ) -
Al (O ₂ Hg) ₃ - -3714 (260)
. 5657,. (256)
2571, ("180)
, 1157, (.81) 1 * 74
·. . Λ ·. . ■. . . . , ■ '1 * 01
■ 1.58
1 * 60,. "'
1, -67 0.2?
0 * 28,
Ö.2Ö
0 * 19 '., >
i
>
ν
V
V
( ■ ^q i2 ^H 25 ^M S ^Br (A-) ¹ -60 ^! "vice versa" JAi (^ i ₇ H '
Al (iC ₄ H ₉ ) ₃
Ul (C ₂ H ₅ ) '274Ο (192)
2357. (Ί65)
"1657 ./;■ (116) '.
614 (43) ^; . ■ ¹ ^
, .7.2
■ '' 7.1 '- 1 * 75
1 * 59
1.65.
1.68. 0.20;
0.2ο
0.24
0.18 C ₁₂ H ₂₅ MgBr (B) . "direct" Al (C _il H _fi3 ) ₅ 3028 (212). 4.1
• 5 * 0
5.5 "'
2.9; ; 1.5? 0.1-5 C ₁₂ H ₂₅ MgBr ■: (C;) ■■ · ... gO., "vice versa" ; ^{A-1 <ö} ll ^fl S2b . 3057 (214)
2786 ■. (195) 5 * 6: ■ IvS? .
1.65 0.21, ■
0.52 C ₄ H ₉ MgBr (3) j -60 "vice versa" | Αΐ (σ ₈ Η ₁₇ ) ₃ 2000 (140) 11.0
6.6 1.66
Ί 0.2-5 '2.5

Claims (15)

Patent claim 1. / Process for producing an olefin polymer by contacting the olefin monoiner with a catalyst produced by reduction of a transition metal compound in their normal highest valency level with an organometallic compound and has been activated with an organometallic compound, characterized in that the Reduction of the transition metal compound at a temperature below 0 G with an organomagnesium compound performs and as an activator a Trihydrooarbylaluminiuinver binding used. 2. The method, in that use according to claim 1, characterized geke η η ζ calibration net as ethylene olefin monomer or a mixture of ethylene and a higher 1-olefin. 3. Method n _r ch claim 1 oder.2, characterized in that a compound is used as the magnesiuinorgai.ische compound which is essentially free of iitheraten. 4. The method according to claim 1 to 3, characterized g e - ke η η ζ eic Ii η et that the reaction product of Llagenisummeta] 1 and a hydrocarbon halide is used as the magnesium compound. 5. The method according to claim 4, characterized in that ο η η - ζ eich η et that / the reaction between Magneniumineta 1.1. and colloidal hydrogen halide carried out in such a way that the organic magnesium product is obtained as a solution. 0 0 9 8 3 1/1 7 A 9 _B AD ORIGINAL ^'00 " 1A-37 330 6. The method according to claim T to 5, characterized in that that one can reduce the transition metal compound of their normal maximum "valence level performed at a temperature not higher than -p0 ° 0. 7. The method according to claim 6, characterized ge k .e η η - draw t that the reductone passes through at a temperature which is not higher than -60 C. 8. The method according to claim 1 to 7, characterized in that there is used as the transition metal compound a 4-value titanium compound is used. 9. The method according to claim 8, characterized in that g e k e η η, that titanium tetrachloride is used as the transition metal compound, -10. Process according to Claims 1 to 9, characterized in that dian is a trialkylaluminum compound as the activator verv / ends., · 11. The method according to claim 10, thereby g e k "ο η η * - draws that as trialkylaluminum compound a connection. of the formula AIR, used in which each R ' is independently an alkyl group having a chain length greater than 4 carbon atoms. ■ 12. The method according to claim 11, characterized in that g e k e η η, that each R is independently an alkyl group with one - chain length g.e; of at least 8 carbon atoms means. 13. The method according to claim 12, characterized ge k eη η - ζ e ic hne t that each R is independently an alkyl group with an Xe btenl.Jinge · ■ ". Vun at least 1! Carbon atoms. ■ .- ■ - ■■ _ -21- 00983 1/17 49 / 1A-37 330 14. The method according to claim 1 to 13> thereby g e ■ indicates that the reduction is carried out in such a way that that the transition metal compound au the magnesium compound admits. 15. Use of the olefin polymers prepared according to claims 1 to 14 for the production of moldings. BAD ORiGINAL 009831/1749