DE1645333C - Process for the production of solid homopolymers or copolymers of ethylene and a catalyst for carrying out this process - Google Patents

Description

in which R is a hydrocarbon radical having 1 to 8 carbon atoms, X is a halogen atom and 11 is a number above 0 and below 3.

5. Catalyst according to claim 4, characterized by an additional content of an alcohol, Ether, amine or alkali metal halide, the amount of this component in moles being the amount does not exceed the aluminum compound in moles.

6. Catalyst according to claim 4 or 5, characterized in that the vanadium phosphate used by impregnating or soaking a pentavalent vanadium phosphate with a hydrocarbon, an alcohol, an aldehyde or an aldehyde polymer and drying and Heating to a temperature in the range of 250 to 600 C has been obtained. fio

Solid, macromolecular polyethylene is widely used. Due to his excellent <> 5 The moldings made from it have distinguished chemical and physical properties high practical weri.

The high pressure polymerization process is used to produce macromolecular polyethylene using radical-forming., η initiators, the low-pressure polymerization process using reaction products from over transition metal halides and organometallic compounds and one carried out at medium pressure Polymerization process used in which the main component of the catalyst is a transition metal oxide is used. However, these procedures are not yet satisfactory in various respects Wishes. Since the high-pressure polymerization process requires "- r" "; ^ L" r.Kprtialh 1000 at, the Reaction vessels must be resistant to extreme pressures. In the low pressure polymerization process, he which a catalyst made of titanium tetrachloride and an aluminum alkyl compound is particularly effective is viewed, the activity of the Kataly fluctuates sators within wide limits depending on the manufacturing conditions, while the activity in the course of the dei The time during the implementation decreases sharply and the life of the catalyst is relatively

is short.

For the medium pressure polymerization process in situ typical catalysts a molybdenum oxide Aliimi niumoxydkatalysator (USA.-Patent 2 691 6-Γ as well as a chromium oxide-silicon oxide-aluminum foil Catalyst (Japanese patent specification 2491 19> "Ί These catalysts are durable, but their catalytic activity is lower than that of the Low pressure polymerization process of catalysts used.

In Japanese Patent No. 412,866, he wrote that one can use olefins with a catalyst can polymerize, the t from Vanadylorthophusph t and a hydride or an organometallic Ver bond of a metal from group I to III of the perm den system. In this procedure, however, the effectiveness of the catalyst is low. As for the polymerization of ethylene, so is off Examples 1 and 2 of this patent can be seen, dal the polymer only in an amount of less than ten times the amount of Vanauylorthophosphhal is obtained.

Furthermore, from an article in the »Journ. brazen Soc. Japan, ind. Chem. Sect. (Kogyo Kagaku Zasshi) " Vol. 66 (1963), pp. 841 to 846, reported in Chemischer Zentralblatt 1965, Issue 49, Referat No. 2603. ready: a process for the production of solid ethylene polymers by polymerization of ethylene ir Presence of catalysts from aluminum triethy and one by calcining in hydrogen strone reduced vanadium phosphate known.

The experiment mentioned in this publication with the vanadium phosphate are also described in the above-mentioned Japanese patent specification 412,866. The V-phosphate-Al (C ₂ H ₅ ) catalyst has as little activity as the catalyst described in the Japanese patent. Polyäthylci z. B. only in an amount of less than de ten-fold amount of the used V-phosphate preserver _t s. In Example 2 of this patent specification, cii <maximum yield after 3 hours of reaction is nu 4.1 times the amount.

The invention now relates to a process for the production of solid homo- or mixed poly Mcrisatcn of ethylene by polymerization before ethylene, alone or together with other poly

merizable olefinic comonomers, in the presence of catalysts made from vanadium phosphates, in which the valence of the vanadium atom is less than 5 is, and organoaluminum compounds which is characterized in that in the presence a catalyst is polymerized, which consists of a vanadium phosphate, in which the mean valence of the vanadium atom is at least 4 and less than 5, and a compound or a mixture the mean composition of general research

consists in which R is a hydrocarbon radical with 1 to 8 carbon atoms, X is a Haloeenatnm nn ^., «;.," Number above (I and below 3. _1S

Subject 1 : The invention is also a catalyst for carrying out the method according to claim 1, consisting of a mixture of a vanadium phosphate, in which the mean valence of the yanadine atom is at least 4, but less than 5, and a compound or a mixture the mean composition of the general formula R _n AlX,

in dei R a hydrocarbon! with I to S carbon stot atoms. \ is a halogen atom and / 1 is a number above π and below cal is 3.

The method of the invention is free from the above mentioned disadvantages of the known methods, d. h .. it does not require h > low pressures, and it becomes a catalyst system with high activity used, the activity of which is comparable to the activity of the usual catalysts for the low pressure procedure, but in terms of its stability and durability comparable or superior to the is the catalyst used in the medium pressure process. tin is another advantage. that according to the invention Process the catalyst residues can easily be removed from the polymers. Furthermore, the molecular weight of the polymers can be determined by the process according to the invention easy to control.

According to the process of the invention, much higher yields are obtained (more than 100-fold Amount, based on the catalyst used) than those from the publication in the »Journ. former Soc. Japan, ind. Chem. Sect. (Kogyo Kagaku Zasshi) «. Vol. M> (1963). Pp. 841 to 846. known methods (see the examples below). The catalysts used in the process according to the invention Sators are responsible for this. They have the further advantage that they can easily be used in dilute acids are soluble, which is important for the work-up of the PolymerisaU is of essential importance (cf. the further inteii following statements). , s

In the calcination of V-phosphate in the H _: stream (5 hours, 500 ° C.) carried out according to the publication mentioned, the vanadium is reduced to the trivalent stage. To produce the V-phosphate used in the invention, the reduction must be carried out under special conditions if one wants to obtain reproducible results, ie a valency of the vanadium within the range mentioned.

The above general formula R _n AlX, _ "\ s p. Indicates the average composition and includes i-.ik'h mixtures of an organoaluminum compound and a halogenated aluminum compound.

The catalyst used in the process according to the invention therefore consists essentially of 2 components, namely a vanadium phosphate and a halogenated organoaluminum compound. The following is the vanadium phosphate as the first catalyst component and the halogenated organoaluminum Compound referred to as the second catalyst component.

A vanadium phosphate of a composition is used as the first catalyst component the general formula

(V ₂ O _y ) (P ₂ O ₅ ) _Z

Vanadium atom means and which is a number with a value not less than 4 and less than 5. and Z is a positive number with a value less than 10. Vanadium phosphates conforming to this formula include the partially reduced products of pentavalent vanadium salts of various phosphoric acids and the partially reduced products of vanadyl salts of various phosphoric acids containing pentavalent vanadium. A typical example is the partially reduced product of vanadyl (V) orthophosphate. This compound has the general formula V, O> P ₂ O ₅ , which corresponds to the aforementioned general formula in which Z has the value I. Similarly, the partially reduced products vi: n vanadyl (V) salts of condensed phosphoric acids can be used, such as vanadyl (V) pyrophosphate. Vanadyl (V) metaphosphate and vanadyl (V) polyphosphate. In these compounds, the mean valence of the vanadium atom must be not less than 4 and less than 5

In the process according to the invention, the aforementioned are wcden Vanadium phosphates are generally used alone as the first catalyst component, it can but also applied to an oxide or a phosphate of a metal other than vanadium Vanadium phosphates can be used. These supported catalysts are made by mixing, produced by coprecipitation or by separation.

The first catalyst component can have been prepared in various ways. For example it can easily be achieved by preparing a pentavalent vanadium phosphate and then reducing it of this product.

The pentavalent vanadium phosphate can be obtained by reacting a pentavalent vanadium compound with phosphoric acid or a phosphate. As pentavalent vanadium compounds can Vanadium pentoxide. Vanadyl (V) trichloride and metavanadates such as ammonium metavanadate and sodium octavanadate or vanadic acid derivatives such as ethyl vanadate. be used. As phosphoric acids can Orthophosphoric acid and condensed phosphoric acids such as metaphosphoric acid. Pyrophosphoric acid and Polyphosphoric acid can be used. As phosphates, ammonium salts and various metal salts can be used of phosphoric acid are used: in particular, water-soluble phosphates or acids are preferred. The aforementioned reaction can not only be carried out in a solvent such as water or alcohol, but also carried out directly without a solvent at room temperature or at an elevated temperature will. For example, vanadatophosphoric acid can be obtained by reacting phosphorus

phosphoric acid, which contains a small amount of water, with vanadium pentoxide. The product is a crystalline one Substance of the following formula

—O O O O—

\ ll II / ν — ο — ρ

—Ο

The first catalyst component is obtained by reducing a pentavalent vanadium phosphate, obtained by the aforementioned procedure. The reduction can go through Heating the product can be carried out in a wide variety of reducing atmospheres, for example the reduction can be carried out in such a way that the mean valence of the vanadium atom in the product obtained is not less than about 4. but less than 5 by converting it into a Atmosphere of hydrogen. Carbon dioxide or sulfur dioxide heated. The heating temperature and time must be set according to the type of reducing atmosphere. If the heating in the Hydrogen flow is carried out at a temperature above 500 C for a longer period of time, sometimes occurs too much reduction and the catalytic activity is decreased. The heating conditions are varied to control when an inorganic reducing gas is used. On the other hand, it was found that the reduction can be easily controlled if you have a pentavalent vanadium phosphate in the presence an organic compound and that the first catalyst component is heated according to this process always gets in high activity.

As organic compounds that are used for the reduction, z. B. hydrocarbons, such as benzene and toluene, alcohols such as methanol. Ethanol, propanol and butanol, aldehydes such as formaldehyde and benzaldehyde, and low molecular weight polymers of aldehydes such as paraformaldehyde, paraldehyde and trioxane, in question. In this case the pentavalent vanadium phosphate is mixed with the organic Compound soaked or moistened or mixed, then dried and finally brought to a temperature heated in the range of 250 to 600 C in air or in an inert gas.

The mean valence of the vanadium atom in the first catalyst component can be quantitatively spectrophotometrically, determined polerographically or by the oxidation-reduction-titration method will.

The mean valence of the vanadium atom in the first catalyst component characteristically has a value of not below 4, but below 5. This means that the first catalyst component consists mainly of tetravalent and pentavalent vanadium phosphates. If the mean valence of the vanadium atom is 5, that is to say if the compound does not contain tetravalent vanadium atoms, the performance of the catalyst is lower. On the other hand, if the mean valence of the vanadium atom is below 4, the effectiveness of the catalyst is not only slightly lower, but the catalyst residue is insoluble in acids and can only be removed from the polymers with difficulty. In the process according to the invention, however, the catalyst residue is soluble in acids In the conventional medium-pressure process for the polymerization of ethylene using a metal oxide catalyst, the catalyst component is insoluble in acids, so the polymer must be centrifuged or filtered off from the catalyst in the molten state or in solution Compared to this process, of course, the separation of the catalyst residues by treatment with acid has considerable advantages,
A compound which has both a halogen-aluminum bond and a carbon-aluminum bond is particularly effective as the second catalyst component. It becomes halogenated

aluminum orean compound or a mixture is an organoaluminum compound and a halogenated one Aluminum connection used. This Compound or mixture can be represented by the general formula

air ^ in which R is an aliphatic or aromatic hydrocarbon radical with I to X carbon atoms and X is a halogen atom and η is a number with a value above 0 and below

3 ~ 3 is.

Examples of halogenated organoaluminum compounds are dialkyl aluminum halides. Diphenyl aluminum halides, Alkyl aluminum sesquihalides. Alkyl aluminum dihalides and phenyl aluminum

vi minium dihalides such as diethyl aluminum chloride. Diisobutyl aluminum chloride, diisobutyl aluminum bromide, diisobutyl aluminum iodide, ethyl aluminum sesquichloride, ethyl aluminum dichloride and diphenyl aluminum chloride.

A mixture of an organoaluminum compound and a halogenated aluminum compound can be used, e.g. B. a mixture of an aluminum trialkyl and a halogenated aluminum compound. Self-

4 <'Understandably, mixtures of the aforementioned various halogenated organoaluminum compounds and a halogenated aluminum compound or an aluminum trialkyl compound can also be used. Examples of aluminum trialkyl compounds are aluminum triethyi. Aluminum tributyl and aluminum trihexyl. Examples of halogenated aluminum compounds are aluminum chloride, aluminum bromide and aluminum iodide.
The amount of each catalyst component used is adjusted according to the capacity of the reaction container, the amount of the solvent, the reaction pressure and the reaction temperature. The first catalyst component is preferably used in amounts of 0.1 to 10 parts by weight and the second catalyst component is used in amounts of 0.5 to 50 parts by weight per 1000 parts by weight of monomer.

The catalyst used in the process according to the invention consists of the aforementioned 2 components

<*> ncnten, but its activity can be improved by adding an alcohol, ether, amine or alkali metal halide as a third component, the amount of this third component, expressed in moles, not the amount of the second catalyst

⁶ s component exceeds.

According to the polymerization process according to the invention, ethylene, alone or together with other olefins, in the presence of the foregoing

Polymerized catalyst. The polymerization will preferably carried out in the presence of a diluent. Suitable diluents are aliphatic, alicyclic and aromatic hydrocarbons and halogenated hydrocarbons such as propane. η-butane. n-Pcntan. n-lleptan. n-oetan. iso-octane. Cyclohexane. Methylcyclohexane. Benzene. Toluene. Xylene. Tetrahydronaphthalene. Decahydronaphthalene, nilorbenzene. Tetrachlorethylene and carbon tetrachloride. The diluents can be used alone or in admixture. For example Any petroleum fraction can be used without further processing, such as gasoline. Luminous petroleum or heavy fuel. Preferably, however, these diluents will become polar contaminants separated, for example, oxygen. nitrogen or contain sulfur and which can react with the catalyst.

The polymerization is expediently carried out at a temperature in the range from 0 to 30 ° C., preferably between 30 and 180 ° C. and at an ethylene pressure of from 1 to 200 kg cm ', preferably between 5 and It) 0 kg em ² . At 0 to 100 ° C., the catalyst is preferably suspended in a diluent. In this case, the polymer separates out in the form of a slurry. At temperatures between 120 and 300 ° C., the polymer dissolves in the diluent as the polymerization reaction proceeds. In this case, the catalyst can be suspended or applied to a support, ie. the polymerization is then carried out in a fixed bed. Furthermore, the process according to the invention can be carried out batchwise or continuously.

The interpolymerization of ethylene with monoolefins such as i-olefins with 3 or more carbon atoms, or diolefins. can be easily carried out according to the method of the invention. For example, you can ethylene with propylene. Butyn-1, 3-methylbutene-1, octane-1 or hexadecene-1 mixed polymers. Copolymers with excellent processability and different physical properties can be produced by copolymerizing small amounts of the aforementioned -olefins with ethylene. Crosslinkable copolymers can also be prepared by copolymerizing a small amount of a linear or cyclic diolefin with ethylene. For example, ethylene can be mixed with butadiene, piperylene, isoprene, 1,5-hexadiene, cyclooctadiene by the process according to the invention. Copolymerize dicyclopentadiene or vinylcyclohexene. Ethylene can also be copolymerized with styrene or its derivatives.

After the polymerization has ended, the catalyst residue can easily be removed from the solid polymer separate by treatment with a mixture of alcohol and an acid. When using a Carrier or a metal compound which is insoluble in acids, together with the first catalyst component, you have to through the solid polymer Heating in a solvent, e.g. B. dissolve a hydrocarbon and then the catalyst residue separate in a conventional manner, e.g. B. centrifuge or filter off.

Homopolymers or copolymers of ethylene with a very high molecular weight can be produced by the process according to the invention. Average molecular weights of 300,000 to 5,000,000 or more can easily be obtained. This macromolecular polyethylene is particularly suitable for purposes that require high impact strength. Abrasion resistance and corrosion resistance matter. For example, the polymers produced according to the invention are suitable for the production of machine parts and in the construction industry.

ίο This type of macromolecular polymer has however, in the molten state a poor flowability, so that it is not according to the usual Injection molding or Slrangprcßverfahren can be deformed.

is For this type of polyethylene, the Compression molding applied. If necessary, the macromolecular polymer is built thermally, oxidatively or mechanically. to be able to use it.

The average molecular weight of the polymers produced can be determined by changing the polymerization conditions or by adding suitable Kcltenuberträgercr to the polymerization. In.> B ^ M'.Jetj one can add more suitable Quantities of hydrogen easily produce polymers of the desired average molecular weight. Polyethylene thus produced with an average molecular weight of 10,000 up to 300,000 is suitable for ordinary spraying

jo cast. Extrusion, blow molding or powder molding processes. The ultrared spectroscopic examination of the microstructure of the polyethylene obtained by the process according to the invention showed that it typically contains a much smaller number of double bonds than the polyethylene obtained by the conventional process. This means that only about 0.05 to 0.5 double bonds per 1000 carbon atoms are present in the polymer. Furthermore, the number of methyl groups can be controlled by the choice of the catalyst and the reaction conditions during the polymerization, and a homopolymer of ethylene can easily be prepared which contains less than one methyl group per 1000 carbon atoms. This means less branching of the polymer. The density of the less branched polyethylene is above 0.950, which corresponds to a very high density polyethylene obtained by the conventional process. The examples below relate to

so parts on weight.

Examples 1 to 6

36.4 parts of vanadium pentoxide and 92.0 parts of 85% orthophosphoric acid are placed in a glass container

SS thoroughly mixed together at room temperature in a nitrogen atmosphere and left to stand for 3 days. The yellow, solid product obtained is a vanadium phosphate which contains pentavalent vanadium but is contaminated with excess phosphoric acid. The product is divided into 6 parts, which are washed nv · water, methanol, ethanol, isopropanol or isobutanol in order to separate off the excess phosphoric acid. The samples are then stored for 2 hours at 70 ° C under reduced pressure.

dries. To the two samples obtained by washing with water, 5 percent by weight of paraformaldehyde and trioxane are added and the mixture is mixed thoroughly.

209 634.Ί59

ίο

The resulting mixtures are dried in an electric oven and dry at 400 ° C. for 5 hours Air stream heated. The product is a vanadium phosphate of the composition

V ₂ O ₁ . · P ₂ O ₅

The mean value Y of the vanadium atom, determined according to the Rcdox titration, is below 5, but not below 4.

In a stainless steel autoclave equipped with an electromagnetic stirrer and which has a capacity of 500 ml. 0.1 g of the obtained in the manner described above Vanadium phosphate given. The autoclave is then charged with ethylene under reduced pressure flushed. Then 10 mmol of ethylaluminum dichloride are added or diethyl aluminum chloride together

with 250 ml of n-heptane added. Then ethylene is injected up to a pressure of 40 kg / cm ² . The ethylene pressure is kept constant during the reaction. The reaction is carried out for 3 hours. Unreacted ethylene is then blown off, the solid product is separated off and the catalyst residue is separated off from this by adding a mixture of equal parts of methanol and hydrochloric acid and heating with stirring. After that, will

ίο the product washed several times with methanol and dried overnight under reduced pressure at 50C. The results obtained are in Table * I compiled. The ratio of polymer yield to the amount of the first catalyst component is considerably larger than the examples described in Japanese Patent Publication No. 412,866.

Table I.

1 Ethanol By S picl
4th s Trioxane Production of the 1st Kataly satellite component: 16.0 5.0 orga fish connection Methanol isopropanol Isobutanol Paraform 4.55 aldehyde 4.97 Amount before heating 15.0 Ethyl- 8.0 8.5 5.0 Diethyl average value of aluminum- aluniiniiini V in the product 4.89 dichloride 4.97 4.94 4.93 chloride 2. Catalyst component Ethyl- Ethyl- Ethyl- Diethyl aluminum- 33.1 aluminum- aluminum- aluminum- I 7 nights dichloride dichloride dichloride chloride I /.V Polymer: 22.1 14.2 Yield, g 44.2 41.1 ■ »β τ. IC I Intrinsic viscosity. Zj. 1 dl / g (xylene. 120 C) .... 21.9 0.08 21.0 20.9 13.6 0.21 Number of doubles ties 1000 carbon atoms each 0.09 0.05 0.08 0.12

B eis ρ ie I e 7 to 11, ^ _n ,

ρ-,, · ■. ". . . . ,. ,. ⁴⁵ JA ^{0 ml} "-Heptane used as a diluent.

The polymerization is carried out at 70 ^? C and produced in a manner quinquevalent Vanadinphosphat ethylene pressure of 40 kg / cm ² by stirring for 3 hours is heated under various conditions, the reaction container is a Edehtahlantoklav aufdieseWeiseerhalteneProduktwirdmeinerMenge with elektromagnetisciemSenkrechlrühSr undΓ MFT of 0.2 g used as the second Katalysatorkompo- 50 of a capacity of 300 ml used. The results are shown in Table II.

Table II

7th 8th example
9 10 Il Production of the 1st Kataly
satellite component:
organic connection...
Amount before heating
the atmosphere
Temperature, "C
7eit hours
Average value of V
in the product 300
5
4.76 H,
350
5
4.19 «
Methanol
17th
N ₂
400
5
4.52 Methanol
17th
N ₂
300
5
4.84 Methanol
17th
air
300
5
4.90

continuation

7th K example
9 Ki Il Polymer:
Dent g 24.5 29.6 25.2 27.6 25.3 Intrinsic viscosity. dl / g
(Xylene, 120 "C) 11.3 9.6 11.3 12.4 13.1

Examples 12 to

The experiments are carried out in the same way as in Example I, but the second Kataiysatorkomponcntc is varied. The results are shown in Table III .

Table III

Hot example

2. Catalyst packages

Ethyl aluminum equichloride

Equimolar mixture of ethyl aluminum dichloride and aluminum chloride

2: 1 mole ratio

Mixture of aluminum triethyl and aluminum bromide

Ethyl aluminum equichloride

Diethyl aluminum iodide

Diisobutyl aluminum chloride

Polymer Intrinsic viscosity
(Xylene. 120 C) crowd
G Howl
P. 16.4 !, 2 38.5 8.8 1.3 17.7 12.2 1.6 7.8 12.2 1.9 9.3 8.7 2.1 14.4 13.1 1.7 26.3

Examples 18-21

Using a vanadium phosphate with an average valence of the vanadium of 4.84, which had been prepared in the same manner as described in Example 1, the polymerization is carried out in various diluents. The reaction vessel has a capacity of 300 ml. And the diluent is used in an amount prior to 150 ml. The polymerization is carried out at 70 ° C., an ethylene pressure of 40 kg / cm ² and for 3 hours. The results are compiled in Table IV.

Table IV example

18th

21

1. catalyst component,

2. Catalyst component.

Amount, g

Diluents Polymer yield, g

Intrinsic viscosity, dl / g (xylene, 120 ⁰ C)

0.1

Ethyl aluminum dichloride

benzene

2.8 7.6

Ethyl aluminum dichloride

1.3 toluene

0.2

Diethyl

aluminum-

chloride

Tetrahydronaphthalene

4.9

15.9

0.2

Diethyl aluminum chloride

1.2

Tetrachlorethylene

18.6

12.0

Example 22

11.6 parts of vanadium pentoxide and 173 parts of polyphosphoric acid are thorough under nitrogen mixed together. The resulting mixture becomes HEATER 13 hours at 70 ° C and 7 hours at 90 ⁰ C. The product is thoroughly gewasche initially with methanol and then for several hours at 70 °

1645

'dried. The dried product still contains about 25 percent by weight methanol. The product is then left to dry in an electric oven for 5 hours Air stream heated to 400 C. The mean valence of the vanadium in the product is 4.53.

0.2 g of the aforementioned product are placed together with 1.2 g of diethylaluminum chloride and 150 ml of n-Hcptane in a reaction vessel with a capacity of 300 ml. The polymerization is carried out at 50 ° C. and an ethylene pressure of 40 kg / cm ^{2 for} 3 hours. 7.9 g of polyethylene are produced _la ] _lcn

Example 23

11.7 parts ammonium vanadate and 11.5 parts orthophosphoric acid c are thoroughly mixed together and then for 5 days at room temperature Implementation brought. The reaction product is washed with methanol, first dried and then heated to 400 ° C. in air for 5 hours. The heated product is a dark yellow-green powder. The mean value of vanadium is 4.45. Using this product becomes ethylene in the same way as in example 22. but with

333 fl

81) C polymerizes. There are 15.9 g of polyethylene receive.

H e ι s ρ ι c I c 24 to 27

Ethylene is homopolymerized in the presence of hydrogen under the following conditions:

Capacity of the react

FUNCTION GLASS 300 ml

'Catalyst composite

^ncnlc \ ani.dmpnosph.il

(mutate Wertigkcil

of the vanadins 4.S.
_{() 2g}

² - catalyst composite

^nontc diithylaluminum

chlonci. 1.2

Diluent .... n-1 lepian. 150 ml
I olymcrization temperature

.. ^{mm 70 c}

Ethylene. Parallel pressure. 40 kg air

Reaction time 3 hours

The amount of hydrogen added is varied.

The results are shown in Table V.

Table V

Added amount of H ₂ . 1

Polymer:

Yield, g

Ash content,%

Intrinsic viscosity, dl / g
(Xylene. 120 C)

average molecular weight ") χ ΙΟ" ⁴

Tensile strength, kg / cm ²

Elongation at break. %

Density, g / cm ³

24

0.11

18.5
0.021

9.5
80
307
465

0.9323

example 25th 2f. 11.2 0.22 2.2 5.6 15.8 7.7 0.035 0.016 0.011 1.6 8.0 3.1 8th 66 19th 235 314 254 970 513 570 0.9525 0.9372 0.9462

The mean molecular weight (weight average of the molecular weight! was calculated according to the equation of C) u ch and Kuchler [,] = 2J6 χ 10 * ra _w ° ™ (7.Elertrochem.6Q.218 <1956).

Example 28

Using 0.1 g of vanadium phosphate with an average valence of the vanadium atom of ss 4.84, which had been obtained in the manner described in Example 1, and 1.0 g of ethylaluminum dichloride as a catalyst and 150 ml of n-heptane as a diluent, ethylene is obtained polymerized at 130 ⁰ C and an ethylene pressure of 20 kg / cm ^{2 for} 3 hours. The polymerization is carried out in the dissolved state of the polymer produced. When the polymerization has ended, the reaction vessel is cooled to below 80 ° C. and the solid polymer is then separated off and recovered in the form of flakes. Solid polyethylene with an intrinsic viscosity of 6.4 dl / g in an amount of 2.7 g is obtained.

Examples 29 to 31

Using 0.2 g of vanadium phosphate, which had been prepared in the same way as described in Example 1, as the first catalyst component and 150 ml of n-heptane as the diluent, ethylene is mixed with other olefins at 70 ° C. and an ethylene partial pressure of 40 kg / cm ² copolymerized. The results are shown in Table VI. When propylene or 1-butene is added as comonomer, the number of methyl groups in the copolymer obtained increases. If butadiene is used, the rate of polymerization decreases and the number of double bonds in the copolymer increases.

15th

Table VI

2. Catalyst component.

Amount, g

added olefin

Amount, g

Polymer:
Yield, g

Intrinsic viscosity, dl g (xylene. 120 C) density, g cm ³

Number of CH ₃ groups per 1000 C atoms Number of double bonds per 1000 C atoms.

29

Ethyl-

aluminum-

dichloride

1.3 propylene

4.2

4.6 9.5

0.9205 26
0.2

16

Betspiel 30th

Diethyl

aluminum-

chloride

1.2

Butene-1
5.6

13th
11.1
0.9213

5.6

0.2

31

Diethyl

aluminum-

chloride

1.2

Butadiene 2.7

1.3 9.9

0.9368 <I.
2.8

Claims (4)

Patent claims: 1. Process for the production of solid homopolymers or copolymers of ethylene by Polymerization of ethylene, alone or together with other polymerizable olefinic comonomers, in the presence of catalysts made from vanadium phosphates, in which the valence of the Vanadium atoms is less than 5, and organoaluminum Compounds, characterized in that in the presence of a Vanadium phosphate, in which the mean valence of the vanadium atom is at least 4 and less than 5 is, and a compound or a mixture of the average composition of the general formula RAIX, η 20th consists in which R is a hydrocarbon radical with 1 to 8 carbon atoms, X is a halogen atom and n is a number above O below 3. 2. The method according to claim 1, characterized in that the polymerization in the presence is carried out by hydrogen. 3. The method according to claim 1, characterized in that that the vanadium phosphate used by soaking. Impregnation or mixing of a pentavalent vanadium phosphate with a hydrocarbon, an alcohol, an aldehyde or a low molecular weight aldehyde polymer and subsequent drying and heating a temperature between 250 and 600 C has been established. 4. Catalyst for carrying out the method according to claim 1. consisting of a mixture from a vanadium phosphate, in which the mean valence of the vanadium atom is at least 4, but is less than 5, and a compound or mixture of the average composition the general formula