DE2915078A1 - ETHYLENE COPOLYMERISATES, PROCESS FOR THEIR PRODUCTION AND THEIR USE - Google Patents

Description

Ethylene polymers of medium density can be prepared by copolymerization of ethylene with α-olefins, such as butene-1, in a suspension system in an inert hydrocarbon solvent in the low pressure process at moderate pressure will. In this case, the polymer obtained is deposited on the inner wall of the reactor, causing difficulties occur in terms of heat conduction, stirring and removal of the polymer. In addition, the polymer particles tend to take on larger and irregular shapes, whereby the space yield decreases and difficulties arise in the transport of the polymer. The technical implementation this method is therefore problematic in terms of cost and in various other respects.

Next to it is the polymerization of propylene in liquid propylene as well as its copolymerization with small amounts of other unsaturated hydrocarbon monomers in liquid propylene (hereinafter: polymerization in bulk) has already been intensively researched and is widely used in industry. the Homopolymerization of butene-1 in liquid butene-1 and copolymerization of butene-1 with a small amount other unsaturated hydrocarbon monomers, such as propylene, Decene, or octadecene, in liquid butene-1 is also known.

Nevertheless, the production of ethylene polymers of low or medium density with a predominant ethylene content by bulk polymerization of ethylene with an unsaturated hydrocarbon monomer in the unsaturated hydrocarbon st off monomer as a liquid medium has not yet found any practical application.

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On the other hand, it is known that catalyst systems which contain a compound of a transition metal of groups IVb to VIb in combination with an organometallic compound of a metal of groups I to III of the periodic table (hereinafter: Ziegler catalysts) can be used for olefin polymerization. There are also numerous investigations
have been carried out in which catalysts which have a transition metal compound on a carrier, were used. Here, it has been found that inorganic compounds, for example oxides, hydroxides, chlorides and carbonates of metals _Λ or silicon represent as well as corresponding mixtures or double salts, effective carrier. Examples of these known carriers are magnesium chloride, double oxides of magnesium
and aluminum as well as double oxides of magnesium and calcium *

The catalyst used for the production of polyolefins should have the highest possible catalytic activity. In this regard, the aforementioned catalysts are
but still unsatisfactory. If they are used for the production of ethylene polymers of low or medium density, the difficulties associated with suspension polymerization in inert hydrocarbon solvents continue to arise, so that no technically satisfactory result. is obtained.

In BE-PS 849 503 of the applicant it is described that catalysts, those by combining an organoaluminum compound have been obtained with a solid catalyst component, the latter by applying a titanium and /

or vanadium compound prepared on a solid support

which in turn is the reaction product of an organomagnesium compound with a halogenated aluminum compound and / or a halogenated silicon compound, are highly active catalysts for olefin polymerization.

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Further investigations with these highly active catalysts in olefin polymerization have now shown that they are the Production of ethylene polymers of low or medium density with extremely high activity and without ash removal processes enable when you have ethylene with an unsaturated hydrocarbon monomer in a liquid phase, the containing the unsaturated hydrocarbon monomer is bulk copolymerized. It has also been shown that in the Polymeri sation results in a polymer with improved suspension properties and high bulk density, with less polymer adheres to the inner wall of the reactor.

The object of the invention is therefore to provide a method len, in the case of ethylene polymers with good suspension properties can be produced with high activity by mixing a large amount of ethylene with a small amount of an unsaturated Hydrocarbon monomer in the liquid phase of the Reacts unsaturated hydrocarbon monomer.

The invention relates to a process for the production of ethylene polymers of low or medium density in the range from 0.900 to 0.940, characterized in that ethylene is mixed with another unsaturated hydrocarbon monomer in a liquid phase containing the unsaturated hydrocarbon monomer in the presence of a Copolymerized catalyst system containing an organoaluminum compound and a solid catalyst component which has been obtained by applying a titanium and / or vanadium compound to a solid product, which in turn the reaction product of an organomagnesium compound with a halogenated aluminum compound of the general formula

R ¹ A1X_ .j η 3-η

in which R denotes an alkyl, aryl, aralkyl or alkenyl radical with up to 20 carbon atoms, X is a halogen atom and η has the value 0 "^ η <3, and / or a halogenated SiIi-

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1 cium compound of the general formula

₂
in which R denotes an alkyl, aryl, araucyl or alkenyl radical with up to 20 carbon atoms, X is a halogen atom and m has the value 0 <m <4.

The unsaturated hydrocarbon used in the liquid state monomers are α-olefins with 3 to 8 carbon atoms, e.g. propylene, butene-1, pentene-1, hexene-1 or octene-1, where Butene-1 is particularly preferred.

The ethylene polymers according to the invention are copolymers from a larger proportion (preferably 80 to 99 mol percent) of ethylene and a smaller proportion (preferably 1 to 20 mole percent) of at least one unsaturated hydrocarbon monomer. The density of the copolymer can be controlled mainly by changing the amount of unsaturated Hydrocarbon monomer that copolymerizes with ethylene is varied. The density of the ethylene homopolymers which can be prepared with the catalyst system according to the invention depends on their molecular weight. However, the average density is around 0.96. The density of the copolymers can be reduced at will by reducing the proportion of the unsaturated hydrocarbon monomer used as a comonomer elevated. In order to obtain a polymer with a density within the specified range, 1 to 20 mole percent of an unsaturated hydrocarbon monomer be introduced into the ethylene copolymer. The amount of unsaturated hydrocarbon monomer required for the

^ O the same density is required, but depends on the Type of monomer. There is a general tendency here that a monomer which has a longer side chain after the polymerization, in a smaller molar amount in the copolymer can be introduced. For example, in FaI-Ie the use of butene-1 as a comonomer about 5 to 18 mol percent of butene-1 are introduced into the copolymer in order to an ethylene polymer with a low density of 0.900

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to obtain 0.925, while about 2 to 5 mol percent of butene-1 are required to an ethylene polymer with an average density of 0.926 to 0.940. Since CU-Cg-a-olefins in the copolymerization with ethylene

g differ from one another in terms of monomer reactivity in the presence of the catalyst according to the invention, the ethylene partial pressure to be maintained in the reactor depends largely on the type of C ₃ -C ₈ olefin. On the other hand, the proportion of the unsaturated hydrocarbon monomer to be copolymerized depends on the ratio between the unsaturated hydrocarbon monomer and ethylene in the liquid phase. In other words: a higher ethylene partial pressure results in a higher ethylene content in the copolymer. Copolymers with a certain content of .je unsaturated hydrocarbon monomer units can thus be obtained by changing the ethylene partial pressure in a suitable manner.

According to the invention by bulk copolymerization in one unsaturated hydrocarbon monomer such as butene-1 Polymer suspensions have the opposite of polymer suspensions produced by conventional suspension polymerization processes (or solution polymerization processes) in which the polymerization generally takes place in a liquid saturated hydrocarbon with 5 to 7 carbon atoms is made have been, the advantage that the polymer can be obtained simply by the fact that the unreacted separating unsaturated hydrocarbon monomer.

3Q The necessary procedural steps only exist in copolymerizing a liquefied unsaturated hydrocarbon monomer with ethylene under elevated pressure and recovering and reusing the unreacted monomer after the reaction. In contrast to the conventional Solution polymerization, it is not necessary to separate a solvent, and the feed system of the

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Polymerization reactor can be simplified. The procedure the invention is thus simpler and more economical.

The polymers prepared according to the invention have opposite conventional high-pressure, low-density polyethylenes have various advantages, e.g. higher strength, stiffness, Cold resistance (especially low-temperature impact strength), Melt ductility, stress cracking resistance and a higher softening point. You can thus in the Areas of application for conventional high-pressure, low-density polyethylene, but also in numerous new areas of application.

The catalyst used according to the invention contains in combi nation an organoaluminum compound and a solid catalyst component obtained by applying a titanium compound and / or a vanadium compound has been obtained on a solid product, which in turn is the reaction product of a Organomagnesium compound with a halogenated aluminum compound the general formula,

R ¹ A1X_,., Η 3-n

in which R is an alkyl, cycloalkyl, aryl, aralkyl or alkenyl radical with up to 20 carbon atoms, X is a halogen atom and η the value 0 ^ η <3, or a halogenated silicon compound of the general formula

^R2 rn ^SiX 4-m '

in which R is an alkyl, cycloalkyl, aryl, aralkyl or alkenyl radical

with up to 20 carbon atoms, X means a halogen atom__ and m has the value 0 <m <4 represents.

As an organomagnesium compound can be used for the preparation of the catalyst any organomagnesium compound obtained by reacting an organic halogen compound can be used are available with magnesium metal.

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Γ "1

Preferred examples of such organomagnesium compounds are Grignard compounds of the general formula

R ³ MgX,

in which R is an alkyl, aryl or alkenyl radical with up to 20 carbon atoms and X is a halogen atom, as well as organomagnesium compounds of the general formula

R ³ ₂ Mg.

As the organomagnesium compound, all possible compositions are suitable which are given by the following equilibrium can be expressed:

2R ³ MgX ± = £ R ³ ₂ Mg + MgX ₂ ^ r ± R ³ ₂ Mg.MgX ₂

regardless of whether the organomagnesium compound has been prepared in the presence or absence of ether [W. Shlenk et al., Ber., Vol. 62, p. 920 (1929) and Vol. 64 _r, p. 739 (1931) 1.

R is an alkyl, aryl or alkenyl radical with up to 20 carbon atoms, like the methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, 2-ethylhexyl, phenyl and Benzyl group. Specific examples of suitable Grignard compounds are ethylmagnesium chloride, ethylmagnesium bromide, η-propy! magnesium chloride, n-buty! magnesium chloride, tert-butyl magnesium chloride, η-Amy! magnesium chloride and Phenyl magnesium bromide.

Organomagnesium compounds of the general formula R »Mg can also be used as organomagnesium compounds, as can be seen from the above equilibrium relationship results. Specific examples are diethyl magnesium, Dipropylmagnesium, Dibutylmagnesium, Diamylmagnesium, Dihexylmagnesium, Dioctylmagnesium, Diphenylmagnesium and Dibenzylmagnesium.

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These organomagnesium compounds are produced and used in the presence of an ether solvent such as diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran or dioxane, a hydrocarbon solvent, such as hexane, heptane, octane, cyclohexane, benzene, toluene or xylene, or a mixture of an ether and a hydrocarbon. In this connection, ethers are particularly preferred as solvents.

The halogenated aluminum compound of the general formula

R AlX- includes all compounds with an aluminum η 3-n

Halogen bond (Al-X). Connections with a larger number on halogen atoms give better results, so that anhydrous aluminum chloride is particularly preferred. the halogenated silicon compounds of the general formula

R SiX. include all compounds with a silicon m 4 - m

. Halogen bond (Si-X). Connections with a higher number on halogen atoms give better results, where

Silicon tetrachloride is particularly preferred.

1 2

In the general formulas, R and R denote alkyl, cycloalkyl, aryl, aralkyl or alkenyl radicals with up to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, η-butyl-., Sec Butyl, tert-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, cyclopentyl, cyclohexyl-y phenyl, and benzyl group. X is a halogen atom, for example the chlorine, bromine or iodine atom, η is a number with a value of O < η <3 and m is a number with a value of O 5 m <4. Specific examples of halogenated aluminum compounds are anhydrous aluminum chloride, aluminum bromide, aluminum iodide, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, dibutyl aluminum chloride, butyl aluminum dichloride, dihexyl aluminum bromide and hexyl aluminum dibromide. Specific examples of halogenated silicon compounds are silicon tetrachloride,. Silicon tetrabromide, methylsilyl trichloride, dimethylsilyl dichloride, trimethylsilyl chloride, ethylsilyl trichloride, di-

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ethylsilyl dichloride, triethylsllyl chloride, propylsilyl tribromide, Dipropylsilyldibromid, Tripropylsilylbromid, Dibutylsilyldichlorid, Tributylsilyl chloride and vinylsilyl trichloride.

The catalyst is produced in an inert gas atmosphere such as nitrogen or argon. The reaction between the organomagnesium compound and the halogenated aluminum compound and / or halogenated silicon compound is preferably carried out in a solvent at a temperature of Oe to 1OO ° C, but may also higher temperatures of 10O ⁰ C or applied over it. Suitable reaction solvents are, for example, aliphatic hydrocarbons such as pentane, hexane, heptane or octane, aromatic hydrocarbons such as benzene, toluene or xylene, alicyclic hydrocarbons such as cyclohexane or cyclopentane, ethers such as diethyl ether, dibutyl ether, diamyl ether, tetrahydrofuran or dioxane , as well as mixtures of hydrocarbons and ethers. In this connection, ethers are particularly preferred as solvents.

The organomagnesium compound is combined with the halogenated aluminum compound and / or the halogenated silicon compound in a molar ratio of 0.1 to 10.0, preferably 0.5 to 2.0 implemented. The reaction product is precipitated as a solid.

The product obtained in this way is isolated and can then be used as a carrier. Here you can use the reaction product as such after filtering or after subsequent thorough washing with a purified one Use hydrocarbon diluent or after further drying. On the carrier produced in this way then applied a titanium compound and / or a vanadium compound.

Examples of usable titanium compounds and vanadium compounds are titanium trichloride, titanium compounds are the general

my formula

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1 Ti (OR ⁴ ) ₄ _ _p X _p ,

Vanadium tetrachloride and vanadium oxytrichloride.

4 4

In the formula Ti (OR) ._ X, R is an alkyl or

ft ρ ρ

Cycloalkyl radical with up to 20 carbon atoms or a phenyl group and X a halogen atom, while ρ is a number with a value of 0 <ρ < 4. Specific examples of titanium compounds that can be used are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethoxytitanium, ethoxytitanium trichloride, dietoxytitanium dichloride, triethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, butoxytitanium trichloride, butoxytitanium trichloride, oxytibridium trichloride, trichloride, phenoxytibromide trichloride, and the activity of titanium trichloride, phenoxytibrometroxy trichloride, butoxytitanium trichloride, and the activity, phenoxytibromide trichloride, dipoxytibrium tetroxide trichloride, and the activity, phenoxytibrometroxiditanium,

15 and particle properties is particularly preferred.

The application of the titanium compound and / or the vanadium compound can be applied to the carrier in the usual way, e.g. by soaking, kneading or coprecipitation. A preferred one The method consists in mixing the titanium compound and / or the vanadium compound with the carrier in the absence of a solvent or in the presence of a suitable inert solvent. The loading reaction will preferably at a temperature of room temperature (approx

20 ⁰ C) to 150 ° C carried out. The reaction product is then filtered off, washed thoroughly with a purified hydrocarbon diluent, and then used either directly or after additional drying. The amount of the titanium compound and / or vanadium compound applied to the support is chosen so that the solid product obtained contains 0.1 to 30 percent by weight, preferably 0.5 to 15 percent by weight, of titanium and / or vanadium atoms. The solid catalyst component preferably has a large specific surface area. In the solid catalyst component prepared in the manner described above, the specific surface area is sometimes more than 200 Ta ² Zg.

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As organoaluminum compounds that are used in the inventive Catalyst system in combination with the solid catalyst component are used, e.g. aluminum trialkyls such as triethylaluminum, tri-n-propylaluminum, tri-n-5. butyl aluminum and tri-n-hexyl aluminum, dialkyl aluminum monohalides / such as diethyl aluminum monochloride, di-n-propyl aluminum monochloride, Di-n-butyl aluminum monochloride and di-nhexyl aluminum monochloride, Alkyl aluminum dihalides such as ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride and n-hexyl aluminum dichloride, as well as alkyl aluminum sesquihalides, such as ethyl aluminum sesquichloride, n-propyl aluminum sesquichloride, n-butyl aluminum sesquichloride and n-hexyl aluminum sesquichloride. These organoaluminum compounds can either be used alone or in combination of two

15 or more connections can be used.

The molar ratio between the solid catalyst component and the organoaluminum compound (Ti and / or V: Al) which used for olefin polymerization can vary within wide limits and is usually about 10: 1 up to 1: 1000, preferably 2: 1 to 1: 100.

The catalyst according to the invention has a very high activity and at the same time, the polymerization can be used as bulk copolymerization be performed. For these reasons, the catalyst is very effective in practical use.

There are no difficulties in the inventively produced To achieve polymers a transition metal content of only about 10 ppm or less, sometimes it can even can be decreased to about 2 ppm or below. A catalyst separation treatment can therefore be omitted without the Product quality would be impaired.

When the inventive bulk copolymerization process is carried out in a lower unsaturated hydrocarbon monomer having 4 to 6 carbon atoms such as butene-1,

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. ORIGINAL INSPECTED

the resulting polymer contains only a small amount a fraction that is soluble in the liquid phase, so that neither an increase in viscosity nor a formation of stickier Masses due to low molecular weight, soluble fractions are observed in the polymerization reactor. The polymer particles have good properties and the production capacity per unit volume of the reactor can be increased.

In the process of the invention, the polymerization temperature can be selected as desired in the range from -20 to +120 ° C., temperatures from 50 to 70 ^° C. being preferred. The reaction pressure is preferably in the range from 1 to 100 kg / cm ² , in particular from 10 to 50 kg / cm ² .

The molecular weight of the polymer obtained can be regulated by introducing hydrogen into the polymerization system initiates. Since the amount of hydrogen to be introduced is from The amount added depends on the polymerization conditions and the desired molecular weight of the polymer

20 are controlled.

Usually an inert solvent is used as a carrier for the feed of the catalyst is used. Examples of suitable solvents are aliphatic ^ hydrocarbons, such as Pentane, hexane, heptane and octane, alicyelic hydrocarbons such as cyclohexane and cycloheptane, and aromatic ones Hydrocarbons such as benzene, toluene and xylene.

The examples illustrate the invention. In the examples are the polymer properties are determined as follows:

The butene-1 content of the copolymer results from the Infrared absorption spectrum of a film showing the absorption the band at 762 cm and then the ethyl group content calculated according to the following equation:

S09843 / 087 2

Γ _

L ·. _χ log (I _o / I) _ 18.2,

Here t is the thickness of the sample (cm), d is the density (g / cm ³ ), I is the intensity of the light passing through, I is the intensity of the incident light and C ₂ H _g / 100 OC is the number of ethyl groups per 1000 carbon atoms.

The density and the melt index (MI) are determined according to JIS K-6760, and the bulk density according to JIS K-6721

Example 1 (1) Preparation of the organomagnesium compound

16.0 g of magnesium turnings are used to make a Grignard reagent placed in a 500 ml four-necked flask with Stirrer, reflux condenser and dropping funnel is equipped. The air and moisture in the flask are then carefully displaced with nitrogen. 0.65 moles of n-butyl chloride and 300 ml of n-butyl ether are poured into the dropping funnel, whereupon about 30 ml is dripped to the magnesium in the flask to start the reaction. If not succeeds, the piston crown is warmed up slightly. As soon as the reaction begins, continue to drop in, so that a mild one Response is sustained. After the end of the dropwise addition, the reaction is continued for about 1 hour at 60.degree. C. and then cooled then the mixture to room temperature and filtered off unreacted magnesium with a glass filter. That in that n-butyl ether containing n-butyl magnesium chloride is 1 η Sulfuric acid hydrolyzed and back-titrated with 1 η sodium hydroxide solution using phenolphthalein as an indicator to determine its concentration. A concentration of 2.00 mol / liter is determined here.

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1 (2) Preparation of the solid catalyst component

The air and moisture are carefully displaced by nitrogen in a 500 ml four-necked flask equipped with a stirrer, dropping funnel and thermometer. The flask is then charged with 35 g of anhydrous aluminum chloride, which has previously been purified by sublimation, and it is dissolved in 150 ml of n-butyl ether while cooling with ice. 132 ml (0.264 mol) of the ether solution of n-buty / magnesium chloride obtained in section 1) are then slowly added dropwise from the dropping funnel, a white precipitate being formed. The mixture is reacted with cooling for 1 hour and then at 50 ° C. for 3 hours. When the reaction is complete, the resulting white solid is separated, washed and dried under reduced pressure, whereby 32.5 g of a white product are obtained. 10 g are placed in a 100 ml four-necked flask, immersed in 50 ml titanium tetrachloride and ^{reacted at 130 °} C. for 1 hour with stirring. After the reaction has ended, it is washed several times with n-heptane until the washing solutions no longer contain any titanium tetrachloride, and then dried under reduced pressure. This gives 7.5 g of a solid catalyst component which contains 25 mg of titanium atoms per 1 g of the solid product and has a specific surface area of 230 m ² / g.

(3) polymerization

A 5 liter stainless steel autoclave equipped with an electromagnetic stirrer is completely filled with dry Filled with nitrogen and then charged with 1250 g of butene-1.

Hydrogen is then passed in up to a partial pressure of 2 kg / cm ² and 15 mmol of triethylaluminum are added. The temperature is increased to 50 ° C., whereupon ethylene is passed in up to a partial pressure of 18 kg / cm ² and then 9.9 mg of the solid catalyst component obtained above, which is suspended in 20 ml of heptane, is added in order to

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tion to start. The polymerization is continued for 4.9 hours at 50 ° C., the total pressure being kept constant by feeding in ethylene. After a certain period of time, the polymerization is interrupted with isopropanol and the unreacted monomer is blown off. The polymer obtained is washed with methanol and dried at 60 ° C. under reduced pressure. This gives 559 g of a copolymer which contains 5.5 mol percent of 1-butene, a density of 0.923 g / cm ³ , a melt index of 0.24 g / 10 min, and a bulk density of 0.33 g / cm ³ has. The catalyst activity in this reaction is 11,500 g copolymer / g solid. Hours or 461,000 g copolymer / g Ti.. Hours.

Examples 2 to 6

Using the solid catalyst component from Example 1, the polymerization is carried out as described above. The results are given in Table I.

Examples 7 to 9

A catalyst is prepared as in Example 1. In the polymerization according to Example 1, the in Table II results mentioned.

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cn

Example 2 Amount of
firm
Catalyst
(mg) Table I. Ethylene Partial
pressure·.
(kg / cm ² ) 6th Polymerisation
tjLonstempera-
door "
. ( ⁰ C) PoJLymerisa-
tLonszeit
(H) . I. Example 3 Examples 2 to vo Example 4 ■ 8.7 28 -, hydrogen
Partial pressure
^; . (kg / cm ² j 50 *} ° Example 5 n _r o Triethyl
älüminium
(mmol) 14th 50 4; 7 to Example 6 9.5 9 50 V O
CD 16.2 15th 23 2 60 ¹ I. ² 00 10.5 10 18th 2 50 CO 15th 3 00
-J 10 10 to 15th

N) CD - »Cn O

CXi

co ο

NS

cn

Table I - Port Setting

yield Butene-1-
Salary .
ftlol-%) density
(g / cm ^J ) " Melting
index
(g / 10 min) Schütt
density
(g / cm ³ ) Catalyst activity g-copolymer 449
641
609
632
613 2.5
10
17th
4.3
⁵ J ³ 0.933
0 _; 912
0.902
0 ₇ 926
0.923 0.09
0 _f 80
2.1
0.20
3.4 ' 0.33
0.30
• 0.24
0.31
° / 32 g-Copolymeri s at g-Ti-atoms.h- g-solid "h 516,000
496,000
556,000
l, 280,000
584,000 12 900
12,400
13 900
32,000
14 600

to

CD cn

00

ro ο

cn

cn

Table II Examples 7 to

Manufacture of the catalyst ^Rl n ^A1X 3-n ■
ο or
* m ^SiX 4-m Organo-
maghesium
link titanium
link applied
Ti amount.
"(% By weight) Amount of
firm
Catalyst
(mg) Organo-
aluminum-
link"
, (in mol) Example 7
Example 8
Example 9 SiCl ₁ ,
30 ml
AlCl
35 g
SiCl ₁₁
30 ml n-BuMgCl
0.264 mol
n-BuMgCl
0.264 mol
n-BuMgCl
0 _; 264 moles TiCl ₁ , '
50 ml
Ti (OBu) ₁ ,
50 ml
Ti (OBu) ₂ Cl ₂
50 ml 2.2
3.5
3; 2 9.7
19.0 AlEt
15th
AlEt ₂ Cl
15th
AlEt ₃
^: 15

ω ■ α m

to O CD OO

co
cn 8th to
cn Table II cn Examples - Continuation 7 to 9

yield
(G) Polymerization conditions and results density
. (g / cm ³ ) Melting
index
(g / 10
min) Schütt
density
(g / cm ³ ) .. Catalyst activity g copolymer ..Po lymeri -
station
Time 602 Butene-1-
salary
(Mol%) 0.922 0.21 0.34 g copolymer
g-solid '. H g-Ti atoms, h (H) 633 5/8 0.919 0 _; 12th 0 _; 31 11,300 514,000 5.5 716 S _t 6 0.921 0.18 0.30 :, 3.3oo 380,000 2.5 5.9 14,100 Ml 000

* 1. The polymerization conditions are similar to those of Example 1 (1 250 g of butene-1; 18 kg / cm * ethylene; 2 kg / cm ^z is hydrogen; 50 ⁰ C).

2. The catalyst is prepared according to Example 1.

3. In the case of the compound names, Et denotes the ethyl group and Bu denotes the buty group.

N?

Claims (14)

"Ethylene copolymers, process for their production and their use " Priority: April 14, 1978, Japan, No. 44 387/78 Claims VJy Process for the production of ethylene copolymers with a density of 0.900 to 0.940 by copolymerization of ethylene with other unsaturated hydrocarbon monomers in the presence of a catalyst containing a titanium and / or vanadium compound and an organoaluminum compound, 2Q characterized in that as Catalyst component used a titanium and / or vanadium compound supported on a magnesium compound is applied, and carries out the copolymerization in the unsaturated hydrocarbon monomer as a liquid phase. 2. The method according to claim 1, characterized in that a solid product is used as the magnesium compound, which is obtained by reacting an organomagnesium compound with a Aluminum halide and / or silicon halide of the general formulas 809843 / 0.072- ORI0INAL INSPECTED Γ "I. in which R. and R _{2 are} alkyl, cycloalkyl, aryl, aralkyl or alkenyl radicals with up to 20 carbon atoms, X is a halogen atom, η has the value 0 <η <3 and m has the value 0 <m <4 , has been received. 3. The method according to claim 2, characterized in that 3 3 a magnesium compound of the formula R MgX and / or R _o Mg 3
used, where R is an alkyl, aryl or alkenyl radical having up to 20 carbon atoms and X is a halogen atom. 4. The method according to claim 3, characterized in that R is a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, Is 2-ethylhexyl, phenyl or benzyl group. 5. The method according to claim 1, characterized in that titanium and / or vanadium compounds are titanium trichloride, titanium compounds of the general formula Ti (OR ⁴ ) ₄ _ _p X _p in which R is a phenyl group or an alkyl or cycloalkyl radical with up to 20 carbon atoms means, X is a halogen atom and ρ the value O * £ ρ < 4 has used vanadium tetrachloride and / or vanadium oxytrichloride. ² ^ 6. The method according to claim 5, characterized in that is called the titanium compound of the formula Ti (OR ⁴ ). X 4-ρ ρ Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraethoxytitanium, Diethoxytitanium dichloride, triethoxytitanium chloride, propoxytxtane chloride, butoxytitanium trichloride, phenoxytitanium trichloride, Ethoxytitanium tribromide, dipropoxytxtanedibromide or tributoxytitanium bromide are used. 7. The method according to claim 6, characterized in that there is used as the titanium compound titanium tetrachloride. ^L 909843/0872 8. The method according to claim 1, characterized in that the unsaturated hydrocarbon monomer is propylene, Butene-1, pentene-1, hexene-1 or octene-1 are used. 9. The method according to claim 8, characterized in that there is used as the unsaturated hydrocarbon monomer butene-1 . 10. The method according to claim 1, characterized in that the amount of titanium and / or vanadium compound is 0.1 to 30 percent by weight, expressed as titanium and / or vanadium atoms present in the solid product are included. 11. The method according to claim 1, characterized in that the copolymerization at a temperature of -20. to + 120 ⁰ C under a pressure of 1 to 100 kg / cm ² . 12. The method according to claim 1, characterized in that the copolymerization is carried out in the presence of hydrogen performs. 13. Ethylene copolymers obtainable by the process of claims 1 to 12. 14. Use of the ethylene copolymers according to claim 13 for the production of moldings. 909843/0872