DE1180524B - Process for the polymerization of ethylene or propylene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN S / jfflWW> PATENTAMT Internat. Class: C 08 f

EDITORIAL

Number:
File number:
Registration date:
Display day:

German class: 39 c - 25/01

E 14256 IVd / 39 c
June 11, 1957
October 29, 1964

It is known that ethylene and other olefins can be polymerized at relatively low pressures that do not significantly exceed atmospheric pressure if various combinations of aluminum compounds, ζ. Β. Aluminum hydride, aluminum alkyls, e.g. B. trialkyls, alkylaluminum halides, with various reducible metal compounds such as halides, acetylacetonates of metals of groups IV to VI and VIII of the Periodic Table, e.g. B. of titanium, zirconium and iron are used. Also previously reduced metal compounds of this type have been used in the absence of aluminum compounds or other reducing agents. The most effective catalysts for this reaction include combinations of trialkyl aluminum or dialkyl aluminum halide with titanium tetrahalide. Excellent results have been obtained using combinations of triethylaluminum or diethylaluminum chloride with titanium tetrachloride, obtained by simply mixing the catalyst components in suitable solvents at room temperature. These catalysts give high yields of solid polymers of ethylene and other olefins with a high softening point even at pressures such as atmospheric pressure or near atmospheric pressure, while the product is of good quality and high molecular weight. For example, catalyst performances of up to 200 g and more of polymers per gram of catalyst have been achieved with ethylene when operating in the presence of an inert liquid diluent. Normally, in the known processes, paraffin hydrocarbons are used which _{boil in the range of C 5} -C ₁₅ hydrocarbons.

The molecular weight of the polymers so produced can range widely from about 2000 to 300,000 and even up to 3,000,000 and above, as by the intrinsic viscosity by the I. Harris formula (J. Polymer Science, 8, p. 361 [1952]). The molecular weights depend on a large number of procedural variables, many of which are interdependent.

A difficulty common to all low pressure olefin polymerization processes common is the formation of an extraordinarily heavy polymer sludge in the liquid reaction medium at the usual polymer concentrations of 10 up to 25% such a heavy polymer sludge, often of a consistency similar to butter, is difficult to handle; it contributes to the soiling of the apparatus and to the formation of a polymer coating on the walls of the Process for the polymerization of ethylene or propylene

Applicant:

Esso Research and Engineering Company,
Elizabeth, NJ (V. St. A.)

Representative:

Dr. W. Beil and A. Hoeppener,

Lawyers, Frankfurt / M., Antoniterstr. 36

Named as inventor:

Egi Victor Fasce,

Joseph Kern Mertzweiller, Baton Rouge, La.

(V. St. A.)

Claimed priority:

V. St. v. America June 14, 1956 (591 261)

Apparatus and loss of heat transfer efficiency. In addition, the polymer sludge extremely difficult to stir, which interferes with correct regulation of the process. Frequent Shutdowns in the case of continuous operation and considerable shortening of the respective operating time in discontinuous processes are the result. This adversely affects the economy of the low pressure polymerization process.

The invention obviates or at least considerably reduces these disadvantages and offers several other advantages as will become apparent from the following description of the invention.

The invention is a process for the polymerization of ethylene or propylene at relatively low pressures and temperatures in an inert, liquid diluent in Presence of a straight chain α-olefin having 6 to 14 carbon atoms and a catalyst which by contacting a compound of a transition metal of Groups IV to VIII of the Periodic System with an organometallic compound of aluminum or with an alkali or alkaline earth metal or an alloy, a hydride or an alkyl or aryl compound of an alkali or alkaline earth metal has been prepared, characterized in that the straight-chain «-olefin with 6 to

409 709/354

14 carbon atoms in an amount of 0.01 to 3, preferably 0.1 to 1.5 percent by weight, based based on the weight of the diluent. The addition of the specified amounts of straight chain -Olefins having 6 to 14 carbon atoms in the polymerization mixture causes a substantial reduction the thickness of the polymer slurry, making the reaction mixture easy to handle and use stirring is and the soiling of the apparatus and

medium can be used. The olefins can be added continuously or partially to the polymerization mixture or be added together with the ethylene or propylene to be polymerized, e.g. B. 5 by saturating the normally gaseous polymerization feed with the normally liquid gene to be added olefin. However, the addition of the straight-chain -v-olefin having 6 to 14 carbon atoms will do for charging the diluent, the formation of a polymer coating on the apparatus, which is usually in the liquid state, is necessary is turned off. It was also fixed. The same procedure can be used put that the thickness of the polymer sludge to that when the ethylene or propylene in the normal-density the mass of the dry polymer is pre-dissolved in evidence of liquid diluent, there is a drawing, d. That is, the thicker the polymer sludge. The amounts of those mentioned that come into question here is, the lower the bulk density of the dry 15 higher molecular weight olefins are in solvents for Polymers and vice versa. This effect depends on- ethylene and propylene are easily soluble. In all cases it is apparently with the relationship between the particles it is desirable that the higher molecular weight olefins size of the solid sludge particles and the thickness of are added before the polymerization reaction starts. Polymer sludge together, the latter increases, reducing catalyst components from manufac-

when the particle size of the solid sludge particles 20 of excellent applicability are metal grows as follows. In any case, there is this relationship and organic compounds of aluminum: Triiso allows a quantitative assessment of the thickness of butylaluminum, tripropylaluminum and trieth'yl polymer sludge. So experience has shown aluminum. Useful organometallic compounds for a smooth operation and effective fertilization of the aluminum of somewhat lower redu-process regulation, the thickness of the sludge-reducing effectiveness are the following: Dimethyl at least correspond to a bulk density of the polymer of aluminum halide, trimethylaluminum, higher 0.2 g / cm ³ , preferably this should step over dialkyl aluminum halides and trialkyl aluminum. The usual low pressure ethylene compounds which contain alkyl groups with more than polymerization lead to thicknesses of the polymer about 10 carbon atoms. Mixtures of sludge, the bulk weights of the dry poly-3 ° aluminum-alkyl can also be used to reduce, generally not more than 0.1, and often the metal compounds. Even less than 0.08 g / cm ³ . For example, ethylaluminum dichloride and diethyl. According to the invention, particularly in the case of mixtures containing aluminum chloride with successful ethylene polymerization, the thickness of the polymer has been used in order in this way to reduce effective sludge to values that produce the rubble catalysts. Similarly, mixtures of diethylaluminum chloride and triethylaluminum can correspond to weights of the dry polymer of about 0.3 g / cm ^3. be used. All of these connections, as well

Those useful for the purposes of the invention, as well as the processes for their preparation, are well known in the 6-14 carbon straight chain olefins. In general, in addition to atoms in the molecule, such as hexene-1, octene-1, tetra-40, the trialkyl or arylaluminum compounds metal-decene-1, of which octene-1 in particular is found to be the most suitable for the organic compounds of aluminum, the two sludge modifications Hydrocarbon radicals or at least one carbon, hydrogen radical and 1 hydrogen atom as well as one. B. an alkoxy group, chain -olefins with 6 to 14 carbon atoms, 45 halogen atoms, organic nitrogen or sulfur ranges from about 0.01 to 3.0 Ge-containing radical, can be used,
percent by weight, based on the liquid diluent. Other suitable reducing substances are the agents. Within this wide range of all-alkali or alkaline earth metals, their alloys, general applicability, excellent er hydrides and their alkyl or aryl compounds, results with an added concentration of 5 ° as far as they have sufficient stability to produce olefin of about 0, 1 to 1.5 percent by weight obtained. a reaction in the form of its association with a

to allow said reducible metal compound.

For the purposes of the invention suitable compounds fertilize transition metals of groups IV to VIII are to organic compounds, such as halides, oxyhalides, complex halides, oxides, Hydroxides, and organic compounds such as alcoholates, acetates, benzoates and acetylacetonates z. B. added olefins in relatively high concentrations of titanium, zirconium, hafnium, thorium, uranium, centrations, e.g. B. in 1 to 3 percent by weight, based on vanadium, niobium, tantalum, chromium, molybdenum, tungsten

and manganese as well as iron. The metal halides, especially the chlorides, are generally preferred with titanium and zirconium being the most effective 65 of these metals. The following metal compounds are relatively easy to reduce, with only relatively low activation temperatures require: titanium tetrabromide, titanium tetrachloride and

Under these conditions the molecular weight of the polymer is little, if any, affected; there is also no noticeable influence on the reaction rate of the polymerization.

The added olefins of the type mentioned appear to form small amounts of relatively low molecular weight (e.g. <10000) soluble polymer to promote. This is particularly evident when the

on the diluent.

The experimental data indicate that the presence of soluble polymer fractions the Reduced reactor pollution.

The olefins added according to the invention can be combined in pure, concentrated or diluted form with an inert liquid diluent

5 6

Zirconium acetylacetonate. The relatively heavy ones are particularly critical. However, it is preferred that reducible compounds are ferrous chloride, chromium at temperatures of about 0 to 150 ° C, especially chloride and manganese chloride. Also pre-reduced at 25 to 9O ⁰ C to work.

Metal compounds such as TiCl _a and / or TiCl ₂ , pressures of atmospheric pressure or negative pressure

can be used as a catalyst component. 5 up to 250 at have so far been used in low-pressure polymer

Particularly striking results have been obtained in the anation of ethylene or propylene with catalysts using the invention on the ethylene polymerization of the type described above, which was carried out with catalysts may be used, minium, diethylaluminum chloride or mixtures io The reaction is preferably prepared with careful exclusion of oxygen from diethylaluminum chloride and triethylaluminum with stirring in the disals reducing agent with titanium tetrachloride prepared continuous or continuous process. These catalysts can be carried out with care. At the discontinuous working temperature regulated about 5 to 20 minutes, the introduction of the polymer to be polymerized or longer will be pretreated. The optimal pre-15 olefins continued until the catalyst is exhausted treatment temperature for a diethylaluminum and the reaction stops. To a stirring produced even after miniumchlorid and titanium tetrachloride to the formation of substantial quantities of the solid PolyKatalysator is to allow the mers between about 40 and 65 ⁰ C., inert diluent Advantageous will influence of the present invention added to medium, as indicated above. This diluent olefin is, however, independent of these preparatory agents, which are applied under the working conditions treatment. must be liquid, include aliphatic, hy-

The catalysts are very generally by droaromatic and aromatic hydrocarbons, intimate mixing of the reducing component with _z . B. pentane, hexane, higher paraffins, cyclohexane, the compound of the transition metal, preferably tetrahydronaphthalene, decahydronaphthalene, benzene, in an inert diluent, in a non-xylene, halogenated aromatic hydrocarbons, oxidizing atmosphere with stirring. z. B. mono- or dichlorobenzene, ethers, such as dibutyl-paraffinic hydrocarbons, e.g. B. heptane or ether, dioxane, tetrahydrofuran and mixtures thereof, another saturated petroleum component or syn- The concentration of the polymer in the reaction aesthetic hydrocarbon oils are the most suitable mixture can be 10 to 40%. Diluents. Before the above-mentioned higher-30 The amount of the catalyst used can vary molecular olefins to these catalyst mixtures within wide limits, whereby they are given something, one will preferably make sure that the purity of the ethylene or propylene charge that the catalyst components have time with- kung depends. Quantities as small as 0.1 weight react with one another. part of catalyst per 1000 parts by weight of ethylene or

The molar ratio of the organometallic compounds propylene are sufficient if the feed is pure formation of aluminum to form transition metal compounds. For loads that are about 0.01 percent by weight in the catalyst mixture can vary widely. Water, oxygen, carbon dioxide or other acidic like it was pointed out above, this substance compounds are contained in general The higher the desired amount of Mo catalyst of about 0.5 to 5 weight molecular weight, the higher the ratio of the polymer. For example, a 40 percent is appropriate.

preferred molar ratio of alkylaluminum compound after completion of the polymerization reaction

fertilize to titanium tetrachloride for the production of the catalyst z. B. by adding an alcohol, polymers with a molecular weight above 20,000 _z . As isopropyl alcohol or n-butyl alcohol, in Menetwa 0.5 to 6: 1, with molar ratios _as far _as that is about ten to one hundred times the ver-12 of 0.3: 1 are suitable in many cases. If desired, the amount of catalyst used can be completely deactivated. The reaction mixture can then be filtered in order to counteract an undesirable decrease in solvent caused by the addition of the filter cake in a catalyst of the higher molecular weight olefin, such as high percentage alcohol, at about the molecular weight. So as a 50 to 100 ⁰ C in the course of 15 to 60 minutes given molecular weight maintain currency 50 slurried and then filtered again, rend the same time the concentration of the added whereupon the filter cake is preferably increased under vermin-olefin, it may It may be advantageous that the pressure is dried. To increase the ash residue ratio of Al: Ti. in the polymer are thereby to under about

The polymerization process according to the invention reduced 0.05 percent by weight, is below normally e at low pressure 55 The polymers produced according to the invention are Olefin polymerization conditions applied by- carried out by conventional low pressure polymerization, around high molecular weight polymers of ethylene drive produced polymers, especially those with and to prepare propylenes which are known as plastics or molecular weights below about 100,000 in are suitable for similar purposes. In doing so, it can be considered in some ways and in every respect Polymerization through intimate contact of the gas 60 at least equivalent, shaped ethylene or propylene charge with the. .

Catalyst, e.g. B. by introducing it into a catalyst B e 1 s ρ 1 e 1 1

Sator suspension in an inert diluent, a series of experiments was carried out in one plant

be performed. The feed can also be carried out for batchwise operation, woflüssiger form or dissolved in a suitable inert 65 with one 2 to 6 g of a diethylaluminum chloride-titanium diluent, which can contain the higher molecular weight olefin tetrachloride catalyst with a molar ratio of, are fed. 1 used, the catalyst 15 Minumerisationstemperatur still the polymerization Jen at 54 ⁰ C in 400 cm ³ with sodium getrock-: Neither the poly Al to Ti = 1

netem n-heptane pretreated as a diluent, diluted with 2200 cm ^{3 of} n-heptane and polymerized the purified ethylene at a rate of 821 per hour in periods of up to over 5 hours at temperatures of 57 to 60 ⁰ C ^. Experiments I and II were carried out with 1.4 percent by weight octene-1, based on the diluent added to the ethylene charge and in dilute catalyst

Sator solution was added after the catalyst pretreatment is carried out. Comparison results under Addition of a higher molecular weight branched chain olefin, such as diisobutylene, to the ethylene feed and the dilute catalyst solution were obtained in Runs III and IV, respectively. The comparison of the Data from Experiment V is summarized in Table I.

Table I.

Il

Attempt no.

HI I IV I V

(Comparison tests)

Percentage by weight of 1-octene, based on the diluent

feed

Weight percent diisobutylene, based on the diluent

feed

Reaction time, hours

Final solids content, percent by weight

Consistency of the reaction mixture

Reaction rate, grams of polymer per hour per gram of catalyst

Harris molecular weight, molecular weight x 10 ^-3

Percentage by weight of polymer wall covering ***)

1.4 **) 8.7 1.4
0.0

3.0 *) 10.3

22.5

63 0.5 5.33
17.4
easy to stir

21.4 *)

70
0.06

1.95 **)
21.6
1.67

26.8

214
1.5

*) Canceled as required.

**) Calculated value based on the higher molecular weight olefin in the ethylene feed. ***) Based on the entire polymer.

0 0

1.4 0

0 0

1.67 3.33

13.4 thick mud

19.3 322

27.1 *)

106

2.3

The data show no difference in results between the introduction of octene-1 into the Ethylene or in the catalyst solution. The addition of diisobutylene leads to a lower effectiveness of the catalyst and a higher molecular weight and differs in this respect from Addition of a straight-chain, higher molecular weight olefin, such as octene-1. The experiments with octene-1 give high Polymer sludge concentrations; d. H. High solids suspensions, easy to stir Reaction mixtures and a much lower formation of polymer wall coverings.

Example II

Various series of batch runs were carried out under the standard conditions given below carried out:

Catalyst with a molar ratio of (C ₂ H ₅ ) ₂ A1C1 to TiCl ₄ = 1: 1, g 1.32

n-heptane as a diluent (dried with clay and sodium), cm ³ 1000

Catalyst pretreatment none

Placing the hot diluent at 68 ⁰ C with 921 per hour of purified Äthylenbeschickung, 15 minutes

Reaction ^{temperature, 0} C 61.8 to 62.5

Reaction time, hours 2

Purified ethylene feed rate, 92 l / hour

Stirring speed, revolutions per minute 500

Octene (I) was added to the diluent in various amounts. The results are in summarized in Table II.

- Tabel!!

10

VI vn Attempt no. IX X *) mud 27.3 (Comparative vin attempt) 47.5 0.4 Weight percent octene (l), based on the 0.0 0.7 30th 1 4 15.1 Diluents 9.9 6.8 1.4 6.0 10.7 Solids content at the end, percent by weight .... stiffer more touchable 8.1 thinner, easier to stir 26th Consistency of the reaction mixture Mud; mud too low, heavy to ge 6.7 stirable measure to will Reaction rate, grams of polymer each 25th 17th 20.4 Hour per gram of catalyst 9.8 Harris molecular weight, Molecular 73 50 36 weight 10 ~ ³ 2.4 2.0 0.18 Percentage by weight of polymer wall covering Weight percent of soluble polymer **) - 2.4 2.7 (based on the entire polymer)

*) 200 cm ^s catalyst solution was pre-treated prior to dilution and before the addition of octene (l) for 30 minutes at 43 ⁰ C.

**) Obtained by cooling the reaction mixture after filtering off the other polymer. The molecular weight was in experiment VIII 6300.

The data in Table II show the effect of adding increasing amounts of octene (I) to the diluted one Catalyst solution at a concentration of 0.7 to 3.0 percent by weight on effectiveness of the catalyst, the molecular weight of the polymer and the formation of the polymer wall covering. The data in experiments VI to IX with a catalyst that had not been pretreated show a decisive one Decrease in the formation of the polymer wall covering, the formation of more easily stirrable reaction mixtures and the formation of a low molecular weight polymer with increasing octene-1 concentration. The addition of octene-1 in Experiment X with a pretreated catalyst also shows the beneficial effects that translate into a lower molecular weight, thin, stirrable Reaction mixtures and express in lower polymer wall deposit formation. The comparison of the experiments VII, VIII and IX also show the influence of the formation of the soluble polymer on the soil of the reaction vessel.

Example III

Some ethylene polymerization experiments were carried out in a continuous plant with a capacity of 11 and in one with a capacity of 7.61 with and without the addition of 0.25 weight percent octene (I) in n-heptane as a diluent using 0.16 to 0.19 percent by weight (based on the diluent) of a catalyst with a molar ratio of aluminum triethyl to TiCl ₄ - 0.5: 1 under standard polymerization conditions approximately at atmospheric pressure and a temperature of approximately 60 to 63 ^° C. The essential conditions and results of these experiments are summarized in Table III.

Table III

Attempt no.
XIII I XIV I XV I XVI

(Comparison tests)
system
Continuous 1-1 plant I Continuous 7,6-1 plant

XI I ΧΠ

(Comparison tests)

Al to Ti molar ratio

Percentage by weight of 1-octene, based on the diluent

Solids content, percent by weight

0.5 0.5 0.49 0.46 0.25 0.25 0 0.25 10.5 11.0 9.0 9.0

0.44

0.25
5.0 **)

**) Lower solids content due to the lower catalyst concentration, namely 0.12 compared to 0.16 to 0.19 percent by weight in other experiments in 1-1 and 7.6-1 systems.

409 709/354

Table III (continued)

Attempt no.

XI I XII i XIII j XIV I XV I XVI

(Comparison tests) j (comparison tests)

system
Continuous 1-1 plant Continuous 7,6-1 plant

Consistency of the reaction mixture

Reaction rate, grams of polymer per hour per gram of catalyst

Molecular Weight (Melt Index) x 10 ~ ³

Pollution factor *)

Bulk density of the polymer, g / cm ³

Thicker

more voluminous

mud

80
61
10.3
0.07

thinner easily
more touchable
mud

73

47
1.2
0.22

62

60
2.2
0.27

thick

55
80
5.0

pretty fluid

39 83 2.5

38 83 1.2

*) Percentage by weight of the polymer remaining as wall covering in the reaction vessel at the end of the experiment, based on the entire polymer.

The data clearly shows the reduction in polymer wall covering and the improvements the stirrability of the reaction mixture by adding amounts as small as 0.25 percent by weight Octene (l) to the diluent.

Example IV The respective influence of other higher molecular weight Ä-olefins as octene (l), including hexene (l) and Tetradecene (l) were determined in individual batchwise standard tests. The conditions the ethylene polymerization were essentially the same as listed in Example III. The influence of the addition of 1.4 percent by weight of the listed modifying -olefins are in the Table IV is listed.

Table IV

Vl

(Comparison test)

Attempt no.
XVII i XVIII

XIX

Added higher molecular weight x-olefin

Percentage by weight of α-olefin, based on the diluent

Reaction rate, grams of polymer per hour per gram of catalyst

Molecular Weight x 10 ^-3

Polymer wall covering, percent by weight

Final solids content, percent by weight

Consistency of the reaction mixture

no

0.0

25th
73

2.4

quite
thick

Octen- (l) 'Hexen- (l)

1.4

20.6

36

0.18

7.5

thinner
mud

1.4

19.6 48

2.5

7.0

thin mud

Tetradecen- (l)

1.4

41 59 0.05 19.5

thin, easy to stir

The influence of the various added higher molecular weight -olefins is what affects the consumption of the added α-Olefins during the polymerization, the formation of the polymer wall covering and the molar ratio the added -olefins to the polymer, obviously. The preliminary conclusions from the In terms of reducing the formation of polymer wallcovering, data indicate that Octene (l) and tetradecene (l) show an advantage over hexene (l). It is also found that more of the added lower α-olefins with polymerize or co-polymerize with ethylene,

like this by the recovery from the hydrocarbon used as a diluent the product work-up was determined.

Example V

Four standard batch polymerization runs (XX to XXIII) with ethylene as feed were using a catalyst with a molar ratio of untreated aluminum triethyl to titanium tetrachloride = 0.5 to 1: 1 and essentially under the polymerization conditions of

Example III carried out. The influence of the addition of 0.5 to 1.4 percent by weight octene (l) on the Formation of the polymer wall covering and the performance of the catalyst were determined. The full Data are summarized in Table V.

Table V

Attempt no.

XX I XXI I XXII
(Comparison tests)

XXIII

Added higher molecular weight -olefin

Percentage by weight -olefin, based on the diluent

Al to Ti molar ratio

Total catalyst concentration, g / l

Reaction rate, grams of polymer per hour

per gram of catalyst

Molecular Weight x 10 ^-3

Consistency of the reaction mixture

*) The original addition of 1.049 g of a catalyst with a molar ratio of Al to Ti = 0.5: 1 resulted no reaction; when adding 0.52 g of a catalyst with a molar ratio of Al to Ti = 0.5: 1 in the course a slight polymerization reaction took place over 70 minutes.

no

0.5
1.049

47.8
69

thicker
mud

Octene (l)

1.4
0.5
1.569 *)

1.9

Octene (l)

0.5
1.0
1.29 **)

7.8
985

Octene (l)

0.5
0.5
1.049

32.6
33

easy to stir
mud

**) With the originally added 1.049 g of a catalyst with a molar ratio of Al to Ti = 0.5: 1, neither a reaction nor a precipitate occurred during the first 30 minutes; when 0.24 g of an additional Al (C _a H ₆ ) ₃ catalyst was added to increase the Al to Ti ratio to 1: 1, a brown precipitate formed and some polymerization occurred.

Striking differences were found by the addition of octene (1) in the diluent to the aluminum triethyl titanium tetrachloride. In experiments XXI and XXII, after the addition of the catalyst ^{mixture in 200 cm 3 of} diluent to the remaining 800 cm ^{3 of} diluent containing the octene (l), which was preheated to 65 ° C and saturated with ethylene as a charge, even after No brown precipitate, which is so often associated with effective polymerization, was found for 30 minutes. A further addition of aluminum triethyl or an aluminum alkyl-titanium mixture in a ratio of 0.5: 1 resulted in the formation of a precipitate and a certain polymerization effect. These observations indicate that the chemical action of aluminum triethyl is markedly influenced by the addition of octene (1). However, if the catalyst precipitation is obtained at room temperature before the addition of the diluent containing the octene (I) and then ethylene is introduced, a good polymerization effect is obtained.

A comparison of the data below shows the same beneficial effect of octene (I) on the Formation of fine polymer particles and a thin reaction mixture as above for the diethyl aluminum chloride - Titanium tetrachloride catalyst specified.

Table VI

Percentage by weight of octene (l), based on the diluent

Experiment no.
XX

(Comparison test)

0.0

XXIII

Table VI (continued) Experiment no. xxm XX 35 (Comparative attempt) 32.6 Reaction speed, 33 40 Grams of polymer per hour each 47.8 Grams of catalyst 69 7th Molecular Weight x 10 ^-3 Solid content at the end, Ge 13th slim 45 weight percent Consistency of the reaction quantity very thick mix at the end

60

65

0.5

Claims (5)

Patent claims: 1. Process for the polymerization of ethylene or propylene at relatively low Pressures and temperatures in an inert, liquid diluent in the presence of a straight-chain α-olefin having 6 to 14 carbon atoms and a catalyst obtained by contacting a compound of a transition metal of Groups IV to VIII of the Periodic Table with an organometallic compound of aluminum or with an alkali or alkaline earth metal or an alloy, a hydride or an alkyl or aryl compound of an alkali or alkaline earth metal, characterized in that the straight-chain "olefin with 6 to 14 carbon atoms in an amount of 0.01 to 3, preferred wise 0.1 to 1.5 percent by weight, based on the weight of the diluent, applies. 2. The method according to claim 1, characterized in that a catalyst is used the reduced one formed by mixing titanium tetrachloride with an alkyl aluminum compound Contains titanium halide. 3. The method according to claim 2, characterized in that a catalyst is used by mixing titanium tetrachloride with triethylaluminum, the mixing at least partly in the absence of ethylene, propylene or a straight-chain «-olefin with 6 to 14 carbon atoms takes place, has been produced. 4. The method according to claim 1 to 3, characterized in that there is used as a diluent a liquid hydrocarbon, especially n-heptane, is used in the polymerization. 5. The method according to claim 1, characterized in that as a straight-chain «-olefin Octene (l) or tetradecene used. IO Publications considered:
U.S. Patent Nos. 2,726,231, 2,727,024, 728,758,2,731,453; laid out documents of Belgian patents Nos. 533 362, 534 888, 538 782, 543 576, 546 600; The Oil and Gas Journal, May 10, 1954, Vol. 53, No. 1, p. 164. A priority document was displayed when the registration was announced. 409 709054 10.64 © Bundesdruckerei Berlin