DE1942734A1 - Process for the polymerization of alpha olefins - Google Patents

Description

FAHBWERKE HOECHST AG. formerly Master Lucius & BrÜning File number: ■ - Fw 6193

Date: August 20, 1969 - Dr.We / Ku Verfahr en ', for the polymerisation of ^ - olefins n-'

It is known that manijC-olefins and their hybrids according to the Ziegler low-pressure processes can polymerize. One uses compounds of the elements of IV. to Vl. Subgroup of the periodic table mixed with organometallic Compounds of the elements of the 1st to III. Group of the periodic table and generally works in suspension, in the solution or in the gas phase.

Processes are also known in which the catalyst components used in conjunction with an inorganic solid will.

In the Belgian patent specification 65O.679 and the French In patent specification 1. ^ 48.320, hydroxychlorides become more divalent Metals of the general formula MeQHCl with transition metal compounds converted into Ziegler catalysts._High "polymer ·! - cationic yields per gram of catalyst are only achieved when working with a pressure of 20 atm.

In British Patent Specification 1. ΙΑ0.6Λ9 liquid Halogejj, vsi, r; bin, dunge ^ L -von transition metals with oxygen-containing compounds of divalent metals, which are practically free of hydroxyl groups, converted into catalysts for the polymerization of olefins. '

Ale oxygen-containing compound of the divalent metals are oxides, sulfates, nitrates, phosphates, silicates, mono- .. and -Polycerboxylate of magnesium and calcium called.

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The Kotal.ysatorausbätze that with the claimed liatalysatoren . are obtained, despite the elevated polymerization pressures - ■ small amount.

In the art polymerization after Zieglerverfa ^ are lead particularly interesting when at pressures below 10 atm ^high: be achieved * catalyst yields, so that a Vvci'tervf.-r- * processing the polymers without Katalysivtorentf erming possible · is. The remaining in the polymer catalysts may ψ neither cause Verfärbroigen the polymers, nor may ■ corrosion on the Verarbeitungsmasehiiien 'to occur ■.

It has now been found a process for the homo- and copolymerization of olefins ot the general formula R-CII = CH _0, in the "'- R ^{1 is} a carbon Wasserstoff'oder Enwa ss he s toff ir est, se prior to gswei a straight-chain or branched, substituted © or unsubstituted alkyl radical with 1-10 carbon atoms, in solution, in suspension or in the gas phase, at temperatures of 20 to 200 ° C., preferably 50 to 150 ° C., at pressures up to 50 atmospheres, preferably 1.5-20 at, in the presence of a mixed catalyst consisting of the reaction product between a titanium compound and a magnesium compound (component A) and an organoaluminum compound (component B), if applicable under regulation ides molecular weight by hydrogen ', ^: ' which is characterized in that the polymerization is carried out in the "presence of a mixed catalyst, the component A of which is obtained by reacting a tetravalent halogen-containing titanium compound with crystalline high-quality magnesium halides. posed; became. , ',' .- "■

For the person skilled in the art, it was surprising and predictable that the reaction products of crystalline alcohol-containing magnesium halides with chlorine-containing titanium compounds would give rise to particularly active catalysts. Because in the aforementioned Belgian patent ^ 650 ^ 679 aüsdrückiich Ü * is raised that ljei use of * nä it on "weivÄr ti gen hydroxyl"

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or metal compounds containing chlorine groups as active catalysts cannot be obtained from MeO) ICl.

This is how the use of chlorine products also prove to be!:. Li tetravalent titanium compounds with crystalline water-containing magnesia imhaJ ogenideii - such as MgCl .11 0, MgCl Ji ,, Ο odej ~ MgCl ₀ .6 U ₀ O - only prove to be very moderate catalysts in the polymerization of * - oils according to the Ziegler process .

β-

The same also applies to the reaction products of anhydrous Magnesium chlorides not titanium compounds containing chlorine which also only result in poor catalyst yields.

The process according to the invention uses, as component, a titanium-containing reaction product which was produced by the action of a tetravalent halogen-containing titanium compound on crystal 1-alcohol-containing magnesium halide, the unreacted magnesium compound being used in the polymerization. Tetravalent halogenated titanium compounds are used as transition metal compounds for the production of component A, preferably titanium precursors of the general formula TiX (OR), in which η = 1 to k, X = chlorine or bromine, R are identical or different hydrocarbon radicals, especially straight-chain or branched ones Alkyl radicals having 1 to 18, preferably 1 to 10 carbon atoms.

For example its TiCl., Ti (OC H) ₀ Cl ₂ , Ti (OC H _p ) Cl,

n J ₂ CIj ,. Ti (oc H ₇ ) ei, Ti (OiC ₃ H ₇ ) ₂ ci ₂ Ti (OiCIiJCi

Ti (OiC ₄ H _9. ) ₂ C _; 1 ₂ , T (OiCi ₁ H ₉ ) ₃ C1, Ti (OiC ₃ Il ₇ IcI ₃ , Ti (OC ₂ Il ₅ ) Cl ₃ called .

Sometimes it can be advantageous to use the halo-ortho-titanic acid ester of the above general formula in situ by reacting the respective ortho-titanic acid ester with TiCl . or TiBr, produced in the appropriate quantity ratio t: l 1 cn.

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Temperatures of 0 to 200 C are recommended for the implementation, where the upper temperature limit is given by the decomposition stone temperature the respective tetravalent, halogen-containing Titanvei'-bond is specified. Temperatures of 0 ° to 120 ° C

The reaction is expediently carried out in inert diluents. Suitable as such are the aliphatic or cycloaliphatic hydrocarbons customary in the Ziegler-N i ederdrucl ·; process, such as butane, pentane, hexane, heptane, cyclohexanes, methylcyelohexane, and aromatic hydrocarbons such as benzene, xylene; Hydrogenated diesel oil fractions that have been carefully freed from oxygen, sulfur compounds and moisture are also useful.

In many cases it is advantageous to react the halogen-containing titanium compound with the crystal alcohol-containing Perform magnesium compound in different temperature ranges.

So you can add the tetra-ferrous, chlorine-containing titanium compound the crystal alcohol-containing magnesium chloride, for example only once at temperatures of 0 to 30 C with stirring let drip and then then terminate the reaction at temperatures from 6o to 120 G with stirring. .

The reaction product of the insoluble in hydrocarbons Halogen-containing tetravalent titanium compound with the crystal alcohol-containing magnesium chloride is washed several times with one of the above inert diluents in which the The inserted-Titan-IV-connection easily loosens, from not on the Solid fixed titanium compounds freed.

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To prepare component A crystal alcoholic magnesium halides of the general formula MgX .η ROH are used in which X = Cl, Br, J, η = 0.1 -'6, preferably 0.5 -. K and ROH a one multivalent o primary, secondary .o. tertiary alcohol with 1 to 20 carbon atoms,

I preferably 1 to 10 carbon atoms,

means. Particularly preferred is the use of MgCl ₀ in conjunction with monohydric aliphatic alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, Isopropaiiol _v pentanol, octanol.

The representation of the crystal alcohol-containing magnesium halides takes place according to methods known per se. ■

So you can use anhydrous magnesium halide with alcohols in the React molar ratio 1: 0.1 to 1: 6. The magnesium halide containing crystalline alcohol is then placed in a ball mill grind. But it is also possible to implement the magnesium halide with a large excess of alcohol and the Alcohol that is not bound as crystal alcohol is then to be distilled off under reduced pressure.

Furthermore, magnesium alcoholates with hydrogen halides can also be used to prepare the crystal alcohol-containing magnesium halides reacted in the presence of alcohols; B.

Mg (OR) _n + 2 HX = MgX _o .2R0II (X = Cl, Br, J)

The reaction can also be carried out in hydrocarbon / alcohol mixtures Be carried outr alcohol that is not crystal alcohol is bound, is then reduced again under Distilled pressure. '

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The representation of the crystal alcohol-containing magnesium halides can finally also by reacting with magnesium Alcohol-hydrogen halide mixtures take place:

Mg + 2 HX - HgX _o . η ROH + H ₀ (X = Cl, Ur, J)

Alcohol that is not bound as crystal alcohol is used then distilled off under reduced pressure.

Before the reaction with the titanium compound, the crystal alcohol-containing magnesium halide can be mixed with other inert, polymerization-non-inhibiting, inorganic compounds. Suitable as such are hydroxides, sulfates, oxides, carbonates, phosphates, alcoholates, etc. Of metals, e.g. B. Mg (OH), alkaline earth _{phosphates, Mg (OR) 0} , DaO and others

The molar ratio between the crystal alcohol-containing magnesium halide used according to the invention and the inorganic compound is not critical and can vary within wide limits. A range of 1 *: 0.05 to 1: 0.9 _t is recommended, preferably 1: 0.08 to 1: 0.5 »

The titanium content of component A can range from $ 0.00. until ; 0.5 ι preferably 0.01 to 0.3 mmol per gram of component Ä · lie. It can be influenced by the duration of the reaction, the reaction temperature and the concentration of the tetravalent, halogen-containing titanium compound used.

The polymerisation is carried out on the magnesia compound Fixed titanium component, expediently in the field of diets from 0.005 to 1.5, preferably 0.05 to 1.5 µmol per Liters of dispersant or Realitor volume used. In principle, however, higher concentrations are also possible. '

The conversion of the tetravalent titanium compound in the “. Component A in dio pplymerisationsactive, lower valence-

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suitably takes place during the polymerization by the organoaluminum compound (component B) at temperatures of 20 - 200 C, preferably 50 - 150 C,

However, component A can also be treated with the organoaluminum compound at temperatures from -30 to 150 ° C., preferably 0- kO C, before the polymerization, and then used in the polymerization. When using Λ ^ ση chlorine-containing organominium compounds, however, it is expedient to wash the resulting reaction product. This is followed by activation with aluminiumorganisehen compounds at temperatures Vo11 / 2O to 200 C, preferably 50 to 150 ⁰ C.

Component A can also be used before the polymerization with an organoaluminium compound and a low one Amount of a polymerizable olefin at Temperatureli of -30 up to 15O C .. In this way, a catalytic converter is disfigured which contains some polymer. In some cases this determines the particle size, bulk density and particle size distribution of the polymer powder favorably influenced.

As aluminum organic compounds, the reaction products from aluminum trialkyls or aluminum dialkyl hydrides with hydrocarbon residues with 1 to 16 carbon atoms, preferably Al (iBu) or Al (iBu) _H and 4 to 20 carbon atoms containing diolefins, preferably isoprene, used will; for example, aluminum isoprenyl may be mentioned.

Also suitable as component B are organoaluminum compounds containing chlorine, such as dialkylaluminum _{monochlorides of the formula R 0} AlCl or alkylaluminum sesquichlorides of the formula R Al ₉ Cl, where R can be identical or different hydrocarbon radicals, preferably alleyl radicals with 1 to 16, preferably 2 to 12 carbon atoms. Examples are: (C ₂ H) ₂ A1C1, UC ₄ H ₉ V ₂ AlCl ₁ (C ₂ II ₁ J Al ₂ Cl.

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Aluminum trialkyls AlR or * Aluiuiniumdialkylhydrides of the formula AIR II are advantageously used as component B, in which R denotes identical or different carbon radicals, preferably alley radicals with 1 to 16, preferably 2 "to 6, carbon atoms, such as Al (C ₂ H _1. ), AlCCgH) ₉ H, -Al (CJI,.), AlCC ₃ II ₇ ) H ₁ Al (IC ₄ H ₉ ) JJ.

The alurainiuraorganisehe component can be in concentration of 0.5 to 10 mmoles, preferably 2 to 8 mmoles, per liter of dispersant, or per liter of reactor volume. "

The polymerization is carried out in solution, in suspension or in the Gas phase, continuously or discontinuously at temperatures from 20 to 200 ° C, preferably from 50 to 150 ° C. the Prints are up to 50 at, preferably 1.5 to 20 at. In principle, however, higher or lower pressures and temperatures than those specified are also possible.

Especially the polymerization in suspension or in the gas phase is usually carried out at pressures of 1.5 to 10 atmospheres. In this case, 0.005 to 1 nmoles are used per liter of dispersant or per liter of reactor volume, preferably 0.05 to 0.5 mmol, titanium compound. " The Polymerization in solution which is preferred for production of low molecular weight polyolefins (polyolefin waxes) with Vjsp / c values from 0.1 to 0.4 (measured as a 1 "solution in Decahydronaphthalene at 135) is carried out, ei * folg.t ' expediently at temperatures of 120 to 200 C and at a pressure of up to 5 ° atmospheres, preferably 1.5 to 20 atmospheres. For the solution polymerization becomes the titanium compound in one Concentration from 0.05 to 1.5 mmol per liter of solvent used.

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The are suitable for solution or suspension polymerization the inert ones commonly used for the Ziegler low-pressure process Diluents as already described in more detail above for the preparation of component A.

Olefins of the general formula R-CII = CiI can be used as monomers can be used in which R is hydrogen or a hydrocarbon, in particular a straight-chain or branched, substituted one or unsubstituted alkyl radical with 1 to 10, preferably Means 1 to 8 carbon atoms. For example be ethylene, propylene, butene- (l), pentene- (l), 4-methylpentene- (1), Called octen- (l).

It is also possible to use mixtures of the olefins of the above formula especially those containing up to 30 wt.? 6, preferably Containing 10% by weight, one or more comonomers.

Preferably, ethylene or mixtures of ethylene with up to to 10% by weight, preferably up to 5% by weight, of anui'-olefins named formula polymerizes. .

The molecular weights of the polymers can be known Regulate manner, preferably hydrogen is used for this.

For the representation of polyolefins for the extrusion and. Injection molding processing is the polymerization with hydrogen content carried out in the gas phase up to 80 Vol.Jo.

For the production of low molecular weight polyolefins (waxes) on the other hand, the polymerization is carried out with hydrogen contents in the gas phase from 80 - 100 VqI.% through.

The great technical progress compared to the known processes, results in the simpler Polymerisalionsausfuhrriing, because due to the high activity of the catalysts according to the invention already- when printing from. below 10 at very high catalyst yields can be achieved.

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With the aid of the catalysts of the invention, the .for the extrusion or injection molding sector interesting polyolefins blank with jfspez / c Fourth from 0.8 to 6 (as measured in 0.1? Iiirer Deknhydronaphthalinlösung at 135 ⁰ C) represent in so liolter yield that the catalyst can remain completely in the polymer *

According to the invention, for example, when using a Catalyst, which consists of that of the washed reaction product of crystalline alcohol-containing magnesium chloride with TiClj, at a polymerization pressure of 5 at, up to 15 kg of polyethylene per gram of MgCl_ or up to 10 kg of polyethylene per inMol of the magnesium compound fixed titanium compound. at The polymerizations can use higher polymerization pressures even smaller amounts of catalyst can be carried out, since the catalyst yields increase with increasing polymerization diuuclc. '

With the aid of the method according to the invention, it is therefore possible to very simple polymerization processes even at pressures below 10 atm carry out, as in the case of suspension polymerization complex operations such as catalyst decomposition, catalyst removal etc. are omitted. After filtering off the dispersant, the polyolefin is dried and further processed directly. The extremely small amount of catalyst that remain in the polymer , do not cause discoloration of the polymers nor corrosion damage to the processing machines.

The use of the catalysts according to the invention also offers the great advantage that when polymerizing in suspension or in solution with a hydrogen content of more than 80 vol Si in the gas phase, polymers with spec / c values of 0.1-0 , k ( measured in a 1 oq solution in

Decahydronaphthalene at 135 C) is formed in high yield.

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Such low molecular weight polyolefins win as so-called build-up waxes increasing technical interest. Per inMol titanium compound arise in the suspension or solution poly-

merisalion up to 1000 g building wax. According to the known procedures (compare Belgian patent 638.OO7 and 6 / 11.563, and the French patent specification 1.500.0 ^ 6) arise due to the lower activity of the Catalysts only in moderate yield.

Example 1:

· £ Catalyst manufacture

ä) Representation of crystalline alcohol-containing magnesium chloride ..

^ 7> 5 S (0.5 mol). Anhydrous MgCl (shown after Brauer Handbook of Preparative Inorganic Chemistry, Volume I, p. 800 (1960)) and 368 g (8 mol) of ethanol (abs.) were heated to boiling under a nitrogen blanket and with exclusion of moisture. ■

The excess alcohol was then distilled off at 200 torr and at a maximum heating bath temperature of 110.degree. 135 g of magnesium chloride containing crystalline alcohol are obtained which, based on the analytical data, has the formula MgCl. k CH "0H owns.

The magnesium chloride containing crystalline alcohol was ground in a ball mill with exclusion of moisture.

b) Implementation with TiCl ^ ■

70 g of magnesium chloride containing crystalline alcohol (shown according to 1 a) are suspended in 700 ml of a diesel oil fraction (boiling range I30-150 ° C.).

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This suspension is added dropwise over the course of 1 hour

40 with stirring and nitrogen blanketing 189.7 g (1 mole)

. "The suspension is then placed under a nitrogen blanket Stirred for 10 hours at 80 °.

You wash it. Precipitation by decating and stirring at 70 ß times with 5OO ml each of the hydrogenated diesel oil fraction. The diesel oil above the solid should be free of titanium compounds. The volume of the suspension is made up to 900 ml.

The titanium content of the suspension is determined kolorimeteiscli with hydrogen peroxide. _ ..- '■.' ■

1 itil suspension contains 0.04 mm oil titanium compound.

Ί.Ί. Polymer ^ satiönuvon ÄthyJien - _-; ■■ -

a) With a hydrogen content of 15 Vol.ji in the Gas phase

100 liters of diesel oil with a boiling range of 110 to 200 ° C. are placed in a 200 '1-Pfaudler boiler, the boiler contents are heated to 85 ° C. and the air is displaced by flushing with pure nitrogen and hydrogen. Sodami Λν-ird a solution of 54 g (400 mmol) of "Al (C ₂ -Hp ..)" - in 500 ml of diesel oil and 100 ml of the catalyst suspension shown according to Ib (4.0 mmol of titanium compound) is added.

The polymerization is carried out at 8 $ '. It will 5 kg of ethylene per hour and as much hydrogen that the hydrogen content in 'the ·' gas phase I5. /ol.Jo amounts to. The pressure increases in the course of the polymerization ' to about 6 at. After 8 hours the resulting

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Polyethylene separated from the dispersant by filtration and dried. There are 38.5 kg of polyethylene with a. ι spec / c value of 4.2 (measured in 0.1% Dekahydronaphthalinldsung at 135 °) obtained. The contact yield is 9> 6 kg of polyethylene per mmol of titanium compound. 15 kg of polyethylene are produced per gram of MgCl, which wr.de is used to manufacture catalysts. The MgCl content of the polyethylene is K, 0.01 wt. ^.

b) With a hydrogen content of 80% by volume in the gas phase (Representation of build-up waxes).

In a 200 1 Pfaudier boiler, 100 1 of diesel oil are added Submitted to a boiling range of 140 to 200 C, the boiler contents heated to 88 C and the air by purging with displaced pure nitrogen and hydrogen.

A solution of 10 8 g (800 mmol) of Al (CH) in 500 ml of diesel oil and 600 ml of the catalyst suspension shown in Ib (2k mmol of titanium compound) is then added. The polymerization is carried out at 88.degree.

There are 2.6 kg of ethylene per hour and so much hydrogen introduced that the hydrogen content in the gas phase 80 Vo. % is. The pressure rises to about 8 atm in the course of the polymerization. After 10 hours the suspension is cooled to 20 ° and the polyethylene is separated from the dispersant by filtration through a pressure filter.

23 kg of polyethylene with a (spec / c value of 0.4 (measured in 1% decahydronaphthalene solution at 135 °).

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Example 2:

Kat alysato r herstel development:

a) Representation of hagnesium chloride containing crystalline alcohol.

24.3 S (1 g atom) of magnesium are dissolved in 2 ^ 0 ml of ethanol
suspended. At 10 C, Λ30 ml of ethanol containing hydrogen chloride (HCl content
90 g ■ = 2> 5 mol) within k hours. After the evolution of hydrogen has ended, the mixture is stirred at 60 ° C. for 1 hour.

Then the excess alcohol is heated to 200 torr and a maximum heating bath temperature of l'iO C
distilled off. This gives 16 g% crystal alcoholic magnesium chloride due to the analytic data, the formula MgCl has .1,6 ₀ C H_0II. The magnesium chloride containing crystalline alcohol is ground in a ball mill with exclusion of moisture.

b) Implementation with TiCl ^

87 g of magnesium chloride containing crystalline alcohol (shown according to 2 I a) are poured into 65O ml of ■ a ■ diesel oil »*
fraction (boiling range I3O - 150) suspended.

'To this suspension' is added dropwise over the course of one hour at 20 ° with stirring and nitrogen blanketing 275 S (1.5 moles) TiCli. Then the suspension is under Nitrogen blanketing was stirred at 80 for 8 hours. Man washes the precipitate by decating and stirring at 70 ° C 8 times with 500 ml each of the hydrogenated diesel oil fraction. The volume of the suspension is increased to IQOQ ml filled up. 1 ml of suspension contains 0.035 mmol of titanium Link. . , ■

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Ethylene-propylene copolymerization

A 200 liter Pflaudler I boiler turns 100 liters of diesel oil (Boiling range 130 - 150 C), the kettle contents are heated to 85 C and the air is flushed with pure nitrogen and displaces hydrogen. Then there will be a solution of 79 »2 g (ΛθΟ mmol) aluminum triisobutyl in 500 ml Diesel oil and 150 ml of the catalyst suspension shown in FIG. 2b (5 μl 2 mmol titanium compound) were added.

The polymerization is carried out at 8oC. It will kg of ethylene per hour, 6θ g of propylene per hour and so much Hydrogen introduced so that the hydrogen content in the gas phase is 25 Völ.Ji. The pressure increases in the course of the »Polymerization to about 7 at.

After 7 hours, the ethylene-propylene copolymer formed is separated off from the dispersant by filtration and dried.

There are 39 ^ ¹ S of an ethylene-propylene copolymer with a density of 0.9 ^ 9 g cm "and a"'spcz / c value of 4.2 (measured in Ojl ^ o- iger decahydronaphthalene solution at 135-1 The contact yield is 7.5 g of Pclj'- merizate per mmol of titanium compound. 5 polymers are formed per Giramiu MgCl used for the catalyst production. The MgClg content of the polymer is 0.02 CtW. 96

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Example 3

a) Catalyst production

50 g of magnesium chloride containing crystalline alcohol (prepared according to 2Ia) are mixed with 1000 ml of a 1 molar TiCl ₀ (OiC H) n solution in cyclohexane under a nitrogen blanket, and the mixture is stirred at 30 ° C. for 2 hours and then at 70 ° C. for 8 hours. Washing the precipitate by decantation, and stirred at 50 8 times with 800 nil of a hydrogenated diesel oil fraction (boiling range I30 - I50 ^0). The volume of the suspension is made up to 1000 inl. 1 ml of suspension contains 0.075 mmol of titanium compound.

b) Ethylene polymerization "'.

Under the conditions specified in 1 II a, an ethylene polymerization with a hydrogen content in the gas phase of 35 V p \.% is carried out nylt 250 ml of atalysatorsuspension (prepared according to 3 a).

There are 38 kg of polyethylene with a Cspec / c value = 2.0 (measured in 0.1 fig decahydroiiaphthalene solution at 135 C) obtain.

Example k '. - ·

Catalyst manufacture

a) Representation of magnesium chloride containing crystalline alcohol; id

In a suspension of 57 S (0.5 mol) Mg (OC H _r ) _o in 500ml

4u jy £

Ethanol (abs.) Are stirred at 20 ° C ^; Introduced i3.8 g (1.2 mol) of HCl. The alcohol is then distilled off at 200 Torr and a maximum temperature of 120 ° C. 102 g of magnesium chloride containing crystalline alcohol are obtained which, based on the analytical data, has the formula .2, Ί -C ₀ IM) II.
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The crystal alcohol-containing magnesium chloride is under Ground moisture exclusion in a ball mill.

b) Implementation with TiCIi

90 g of magnesium chloride containing crystalline alcohol (shown according to k a) are suspended in 60 ml of a diesel oil fraction (boiling range I30 - 150) «

275 g (1.5 mol) of TiCl are added dropwise to this suspension in the course of one hour at k0 ° with stirring and with a nitrogen blanket. The suspension is then stirred at 100 for 6 hours with a blanket of nitrogen. The precipitate is washed by decating and stirring at 60 ° C. 8 times with 500 ml of the hydrogenated diesel oil fraction each time. The volume of the suspension is made up to 800 ml. • 1 ml suspension contains 0.0 ^ 0 mmol titanium compound.

c) Al (C ₂ H) ₂ C1 treatment

6.0 g (50 mmol) of aluminum diethyl chloride in 50 ml of diesel oil at 25 ° C. are added to 150 ml (6 mmol of titanium compound) of the suspension obtained after 4 b within 60 minutes, while stirring and under a nitrogen blanket. The suspension is then stirred for 2 hours at 25 ° C. and washed k times with 150 ml of diesel oil each time. The ^ volume is set to 200 ml. filled up,.

II Ethylene-Duten- (1) copolymerization

In a 200 1-Pfaudier boiler 100 1 Diesel oil are initially introduced with a boiling range of ΙΛΟ to 200, the contents of the vessel heated to 85 ⁰ C and the air is displaced by flushing with pure nitrogen.

Then a solution of 57 g (ΊΟΟ mmol) of Aluminixuiidiisobutylhydrid in 500 ml of diesel oil and 150 ml of the after k c. . "- 18 - ■

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Catalyst suspension shown (4.5 mmol of titanium compound) admitted.

At 85, 42 kg of ethylene (6 kg / h) ^ and 0.49 kg butene (l) (0.07 kg / h) and so much hydrogen introduced, that the hydrogen content in the .Gasphase 25 Vol.56 is, °

The boiler pressure rises to 5 at at. .

The ethylene-butene copolymer is by filtration from Separated dispersant and dried.

40 kg of polymer with an nspec / c value of 3.9 (measured in 0.1% strength decahydronaphthalene solution) and a density of −Q.948 g cm · ³ are obtained.

The contact yield is 8.8 kg of polymer per mole of titanium compound. Per gram MgCl _0, the "catalyst preparation was used arise 7 fcg'Polymerisat .." - ^DER; MgCl in the polymer is <Q, 02 wt% · The polymer is very good for the extrusion content... suitable for the production of bottles, cables, pipes, etc.

Example· 5 \

Catalyst manufacture

a) In a suspension of XXk -g (1 mole) Mg (OC _n IL) ₀ in 80 ml of a hydrogenated diesel oil fraction (boiling range 140-160) and 46.07 g (1 mol) of ethanol, as much HCl is introduced at 40 with stirring until the weight gain 76 5g "(2.1 moles) is.

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Then it is diluted with 800 ml of diesel oil. Under stirring and nitrogen blanketing are added dropwise within one hour at 25 ° C 550 g (3 mol) _- TiCIj.

The suspension is then blanketed under nitrogen Stirred at 80 for 6 hours. The precipitate is washed 6 times by decanting and stirring at 60.degree per 1500 ml of the hydrogenated diesel oil fraction.

The volume of the suspension is made up to 1.8 liters. 1 ml suspension contains 0.035% iMo-1 titanium compound.

b) Al (C ₂ II _1. ) treatment

To 175 ml (6.1 mmol of titanium compound) of the obtained after 5 a Suspension within 60 minutes with stirring and nitrogen blanketing 3, ^ 1 g (30 mmol)

_% Aluminum triethyl in 50 ml of diesel oil was added dropwise at OC, stirred.

The suspension is then heated to 20 ° C. for 2 hours

II ethylene-butene (1) copolymerization

In a 200 l Pfaudlex boiler, 100 l of diesel oil are used presented with a boiling point calibration of 1% 0 - 200 C, the Kettle contents heated to 75 and the air displaced by flushing with pure nitrogen. Then a solution of 3 ^ 1 * S (3OO niMol) aluminum triethyl in 3OO ml diesel oil and 150 ml of the catalyst suspension shown after 5 hours (4.1 mmol of titanium compound) was added.

+) and so much

Then at 85 C within 8 hours ^; l0 kg ethylene (5 lcg / h), 0.16 kg buteti (1). (0.02 kg / h) ⁺ hydrogen introduced that the Vr. The hydrogen content in the gas cylinder is 35% by volume. The boiler pressure); increases in the course of the polymerisation ciuf, 8 at fin. The ethylene-butene-Cojiolyiuor j sa L is separated from the dispenser by filtration or dried. Kk become co. 38 kg Misc.bpolym ··! isci t with

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one

(, spec / c-V value of 2.9 (measured in 0.1%

Decahydronaphthalene solution) and a density of 0.955 S

-3 '

cm received.

The contact yield is 91.3 kg of polymer per mole ■ Titanium compound. 5 »8 kg of polymer are produced per gram of MgCl. The MgCl content in the polymer is less than 0.02% by weight. The polymer is very good for extrusion processing suitable for the production of bottles, cables, pipes etc.

Example 6:

a) Catalyst production

24.3 g (1 g atom) MagnesiuiTipowder are in 24O ml iso-propanol suspended. At 10 C it is done drop by drop »Addition of 350 ml isopropanol containing hydrogen chloride, (HCl content 90 g = 2.5 mol) within 4 hours.

After the evolution of hydrogen has ceased, it takes 3 hours stirred under reflux. Then Λίχΐ-d dqr. Excess Alcohol distilled off at 200 torr and at a maximum heating bath temperature of 140C.

The residue is suspended in 500 ml of a hydrogenated diesel oil fraction (boiling range I30-150).

This suspension is added dropwise over the course of 1 hour 25 ° C with stirring and nitrogen blanketing 379.4 g (2 mol) TiCl ^.

The suspension is then stirred for 10 hours at 100 ° C. under a nitrogen blanket.

Wash the precipitate by decating and stirring at 70 8th times with 750 ml each of the hydrogenated diesel oil fraction

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tion. The diesel oil standing above the solid should be released of titanium compounds.

The volume of the suspension is made up to 800 ml. 1 ml of suspension contains 0.75 mmol of titanium compound.

b) ethylene polymerization

Under the conditions given in Example 1 II a, an ethylene polymerization is carried out with 50 ml of catalyst suspension (prepared according to 6 a). 38 kg of polyethylene with a Cspec / c value = 5.1 (measured in 0.1% strength decahydronyphthalene solution at 135) and a density of 0.951 g cm ^J are obtained.

Example 7;

in a l6 liter vessel is added 10 liters of diesel oil (boiling range l40 - 170 ⁰ C). After purging with nitrogen and ethylene several times, the mixture is heated to an internal temperature of about 126 ° C .; 50 mmol of aluminum triethyl and 120 ml of the catalyst suspension (Λ, 8 mmol) shown according to lib are then added. 1100 liters of ethylene and 14o liters of hydrogen are introduced per hour with stirring (stirring speed 295 rpm) under a boiler pressure of 18 at hydrogen and 2 at ethylene (pre-pressure: 20 at). With this mode of operation, the exhaust gas consists of 100 % hydrogen. ^{The internal temperature rises to 133-137 °} C. in a few minutes as a result of the exothermic polymerization and is kept at this temperature. After 2 hours, the polymerization is by degassing ml and addition of 500: aborted m-butanol. The mixture is stirred for a further 1 hour, the polymer solution is then steam-distilled with rapid stirring for 1/2 hour and, after the distillation has ended, cooled with stirring. The product is dried at 75 ° C. in a vacuum drying cabinet. 2.5 kg of white, powdery polyethylene wax are obtained.

109809/1987

- ". 22- Fw 6193

RSV: 0.167 dl / g (measured as a 1% solution in decalin at 135 ° C.) Schinelz viscosity ( l ^l 10 °) : 270 / centistokes7; Bulk weight: 420 g / l. ·

Example 8:

As set forth in Example 1, passing in 8 liters of diesel oil (boiling range: l40 -170 ° C) at 13'i - IiO ⁰ C in the presence of 50 mmol triethyl aluminum and 120 ml of B after 4 represents gell prepared catalyst suspension (4.8 mmol) under a boiler pressure of 18 atm of hydrogen and 2 atm of ethylene (pre-pressure: 20 at) in the hour 1700 liters of ethylene and 140 liters of hydrogen; 100% of the exhaust gas consists of hydrogen. After 1 1/2 hours, the gas is degassed, 50,000 ml of n-butanol are added and the mixture is worked up in the usual way by steam distillation. 2.95 kg of white, powdery polyethylene wax are obtained.

RSV: 0.115 (measured as a 1-sequence solution in decalin at 135 C). Schinel viscosity: 100 (centistokes); Bulk weight: '»30 g / l.

109809/193

Claims (1)

... - 23 - Fw 6193 Patent claims: 1. Process for the homo- and copolymerization ofoC-olefins of the general formula R-CH = CH ₀ , in which R is hydrogen or a Approx Hydrocarbon radical, preferably a straight-chain or branched, substituted or unsubstituted alkyl radical with 1 - 10 carbon atoms, in solution, in suspension or in the gas phase, at temperatures of 20 to 200 C, preferably 50 to 150 C ₁ at pressures up to 50 atm, preferably 1.5-20 at, in the presence of a mixed catalyst, consisting of the reaction product between a titanium compound and a Magiiesiuinverbindungen (component A) and an organoaluminum compound (component B), optionally with "regulation of the molecular weight by hydrogen, characterized in that the polymerization is carried out in the presence of a mixed catalyst, component A of which was prepared by reacting a tetravalent halogen-containing titanium compound with crystalline alcohol-containing magnesium halides. rl. Method according to Claim 1, characterized in that crystal alcohol-containing magnesium halides of the general Formula MgX .η ROH, in which X = Cl, Br, I; η = 0.1-6 and ROH mean a mono- or polyhydric, primary, secondary or tertiary alcohol with 1 to 20 carbon atoms, to be used" 3. The method according to claim 1, characterized in that crystal alcohol-containing magnesium chlorides of the general Formula MgCl .11 ROH, in which η = 0.1-6 and ROH is an aliphatic does Alcohol with 1 to 10 carbon atoms means used will. - 2'i - 109809/198 "/ · - 2k - Pw 6193 ¹ I. Process according to claim _1, characterized in that those of the general formula TiX (OU)) are used as four-membered, halogen-containing titanium compounds, where n. = 1 to Ί, X - Cl, Br u «d H are the same or different Kohl onwasperst off residues with 1 to IP »mean carbon atoms. 5 · seduce., Η-ah claim 1, characterized in that one as an organoaluminum compound, aluminum trialkyls Formula Al (R) or Aluniiivumdialkylhydride of the formula H is used, where U is the same or different hydrocarbon radicals means having 1 to 16 carbon atoms. 6. The method according to claim 1, characterized in that Mixtures of ethylene with up to fcu 3O Cc «.? * In Λ -olefins polymerized according to the formula mentioned. 7ν terms according to claim 1, characterized by ge! <That mnn as olefins ethylene, propylene, butene- {1), pentene- (l) or 4-methylpentene- (l) used. 109809/1987