DE1918995A1 - Process for the polymerization of alpha olefins - Google Patents

Description

Process for the polymerization of Φ -olefins.

It is known to polymerize cL- olefins with the aid of catalysts made from halogen-free vanadium, zirconium or titanium compounds with the addition of aluminum trihalides or dihalide hydrides and an alkyl and / or aryl-lithium compound. According to this process, the polymerization is only possible using the three catalyst components mentioned. This method allows polyolefins to be produced with yields sufficient for the industrial scale.

It is also known to use mixtures such as vanadium oxychloride and titanium tetraester to react together with Aluniiniurnalkyl connections and the precipitated reaction product also for Polymerization of ^ -olefins, especially ethylene, to use. When using mixtures of transition metal compounds in the range from 0.5 to 20 mg / l solvent, high yields are achieved on plastics, especially when working under pressure. Optimal yields are obtained when the molar ratio of titanium to vanadium is 1 -: 1 to 1: 5. As it turned out has, but the flow properties of those produced with such catalyst systems are insufficient under these conditions To achieve polyolefins.

The invention relates to a process for the polymerization of ^ -olefins and mixtures thereof with 2-6 carbon atoms, which thereby is characterized in that, to carry out the polymerization, catalysts composed on the one hand of mixtures of halogen-free organic Titanium and vanadium compounds and, on the other hand, one or more organometallic compounds containing chlorine and / or bromine Compounds of I. to III. Group of the Periodic Table with the addition of aluminum trialkyls and / or zinc and / or cadmium compounds are used.

The halogen-free organic titanium or vanadium compounds can e.g. in the form of azoxy compounds, such as titanium tetrapropylate, Titanium tributylate, titanium oxybutylate, vanadium tributylate, .Vanadium tetrabutylate, vanadium oxytripropylate etc. or as end compounds, such as acetylacetonate or phenolates, cr-

009846/1898

sylates, naphtholates etc. are used. Lie use of the Titanium and / or vanadium component in the form of carboxylic acid salts of aliphatic and aromatic monocarboxylic acids, such as acetates, propionates, butyrates, caprylates, Benzc-ate, salicylates is possible. With good success you can also use the salts of Polycarboxylic acids, especially dicarboxylic acids such as malonates, Use maleates, succinates, phthalates, etc. These acids can also carry organic ester groups. Of course It is also possible to use mixtures of the compounds mentioned or compounds which are partly acyl, partly Carry alkoxyl or enolate groups.

The valency level of the titanium and / or vanadium compounds should be at least three before formation. To be favoured Compounds that are soluble in inert solvents.

The reduction can be carried out in any way, so For example, it is possible to use a transition metal compound such as a vanadium oxytriester initially under mild conditions To reduce aluminum haloalkylene to the third valency level, add titanium tetraester and then the mixture Both compounds under more energetic conditions together with aluminum bromoalkylene to the catalytically optimal reaction stage bring to.

You can also submit the organic titanium compound, with aluminum haloalkyl reduce and after adding the vanadium compound with aluminum haloalkyl prepare the catalyst or you go immediately from the transition metal compound mixture.

The additional components e.g. zinc diet and / or cadmium diet, it is expedient to use at the same time as the aluminum haloalkyl in the precipitation of the transition metal compounds, either dissolved in aluminum haloalkyl or by dropwise addition from a separate one Funnel.

It is of course not necessary to use the defined organometallic compounds containing chlorine or bromine as well

^009846/1698

aie define compounds of zinc and / or cadmium for the Use polymerization. Instead, it is possible to use compounds from which, in situ, the organometallic compounds mentioned Connections arise. For example, zinc dialkyl and zinc chloride or Zinc bromide can be used, from which by reaction.Zinc alkyl chloride or zinc alkyl bromide is formed.

The additional components are also after the precipitation or after subsequent formation, possibly also after washing the formed Catalyst added.

The titanium: vanadium ratio can be varied within wide limits. So it is possible to use the catalyst components with good To use the effect in molar ratios from 0.5: 9.5 to 9.5: 0.5.

The aluminum alkyl ratio to the transition metal compound mixture it is expedient to use above 2: 1. But it is also possible to stay outside this relation.

The ratio of zinc and / or cadmium compound: aluminum compound is between 1: 1 and 1: 100, preferably between 1: 5 and 1:40. The catalysts can be used with great success for the polymerization of ethylene and / or d ^ -olefins in dry State to be used.

The yields of plastics when using the catalyst systems according to this invention are excellent and are of the size of the method cited at the beginning using Vandiix> xyhalogenici and titanium tetraester in a ratio of 1: 1 to 5: 1. A particular advantage of the present invention is that? In addition, the excellent flowability of the resulting polymer granules, which makes granulation superfluous.

The production of the catalysts according to the present patent application expediently comprises the following steps: 1.) Reaction of the transition metal compounds with bromine- and / or chlorine-containing organometallic compounds in indifferent Solvents.

009846/1698 bad original

- ■ 4 -

Λη the reaction can Heat a ^ or aging of the · - ₀ emisches reaction, possibly with the addition of further organic aluminum, zinc-.jcnlie'sen at una / OAER Cadruiurn compounds.

In this way u.ar, "eu immediately usable Catalyst. Shall the fibers resulting from the formation are removed, the following steps need to be followed:

2.) Separation of the solid from the liquid components of the • emic. (If necessary also immediately after the precipitation reaction)

3.) Use of these solid catalyst components in combination with aen mentioned additional components for the polymerization.

The heating of the catalyst after formation can take place at up to +200 ⁰ C for a short time (about 1/2 - 8 hours). Voer can also be left to mature for a long time at a low temperature, for example at room temperature.

Solutions are preferably used to form a catalyst in inert media such as aliphatic, alicyclic, aromatic Hydrocarbons, such as H ^ xane, heptane, ifcnane, octane, Cyclohexane, kydrocumene, benzene, toluene, xylene or also nalogenated Hydrocarbons such as chloroform, methylene chloride, trichlorethylene, Perchlorethylene etc. or mixtures of the solvents listed above.

Should be a reactant in the inert solvents do not solve, a formation using a sniffing Rünrer is also possible.

The reaction of the partners can be carried out in a wide temperature range. So it is possible to z-.ß. between - 100 C to +200 ⁰ C to carry out the formation. A temperature between -50 C and +100 C is particularly preferred.

BATH ORIGINAL

0098 46 / 169.8 _;

During the reaction of the organometallic compounds with the transition metal compounds, a brown precipitate falls out, which does not change its color significantly even during the subsequent heating. If the reduction conditions were too severe, E.g. through the use of too much aluminum trialkyl during the formation or the subsequent "aging" black catalyst with lower polymerization activity. *

An example of the combination of the catalyst components according to this invention is given below: A mixture of titanium tetrabutylate and vanadium oxytricaprylate in gasoline is mixed with aluminum alkyl bromide at + 40 ° C. with stirring. added, whereby a dark brown precipitate is formed immediately. To complete the reaction, the mixture is then heated to around 100 ^° C. for about 1 hour. The precipitate which has separated out can be used immediately in this suspension. But it is also possible to separate it beforehand, wash it with gasoline and then react it with fresh aluminum alkyl, expediently aluminum trialkyl with "*" -olefins.

With the catalysts according to this invention polymers can be prepared in Ternparaturbereich from -40 ⁰ C to +300 ⁰ C. The best results are obtained between + 40 ° and 100 ° C. With somewhat lower activity of the catalyst, however, can also be used over 100 ⁰ C, but is between 150 - 16O ° C again a significant drop in activity.

All olefins polymerizable by the Ziegler process can be used with the catalysts according to this patent application. It is possible, for example, to polymerize ethylene, propylene, c ^ -butylene, 4-methylpentene-i, etc. as well as mixtures of these a ^ -01et ine to form high molecular weight plastics.

It was surprising and in no way to be foreseen that the catalysts prepared in this way would be used in a polymerization batch in an amount well below 5 mg Transition metal compound / l solvent still excellent polymerization rates, combined with a very good

0 0 9 8 4 6/1 S Ö 8

BATH

ability of the resulting Polymerisatkorns show the polymers form even after long periods of operation no Bela _o e on the reactor walls u. stirrers. The known methods can be used to regulate the chain length _{3 e.} The use of hydrogen is particularly useful. '-

The special features of the catalytic converters are striking of this application in the polymerization reaction under pressure noticeable. , '"".

With the extremely high polymerization activity of the catalyst combinations . According to the patent application, it is not necessary to Wash polymerizate after reaction with alcohols or other solvents. You get perfect without any purification colorless polymers.

In order to keep the halogen values in the polymers as low as possible, hold, is used as a cocatalyst in the polymerization with precipitated and washed catalysts, if possible halogen-free metal alkyl compounds such as aluminum triethyl or aluminum diethylalkoxyl. When using aluminum trialkyls with short chains (<5 carbon atoms), such as aluminum; triethyl, the concentration should not be higher than about 4 g / l solvent, otherwise the solid mixed contact is reduced noticeably deeper with darkening to black, which is associated with a devaluation. As it turned out through experiments has, with very good success, 0.5 g aluminum triethyl / l Solvents and less are used, If one uses aluminum trialkyl with longer side chains as cocatalyst, -such as aluminum tripropyl, -butyl, -octy1 etc. can also polymerized with higher concentrations than 4 g / l solvent will. When using the different catalysts, different polymerization conditions often arise under the same polymerization conditions Molecular weights (if red value) a. Should now e.g. a polyethylene with certain properties (u red value e.g. 2 - 3) are established, so, depending on the type of catalyst, one often has to vary add large amounts of hydrogen as a chain terminator. Daeber the

009846 / $ 160 BAD ORIGINAL

..hydrogen the activity of the catalysts with increasing concentration inhibits, they can only be compared exactly by measuring the polymer yield per time if one under otherwise the same reaction conditions through the necessary hydrogen concentration sets approximately the same molecular weights. The procedures in the production of some contact combinations, the yields and the physical constants of the polymers When the catalysts according to this application are used, the examples which now follow are illustrative may serve the present invention.

Examples

A) catalysts

Representation of the catalysts

In a 500 ml glass flask filled with nitrogen with thermometer, stirrer, dropping funnel, reflux cooler and A halogen-free titanium and vanadium compound in 100 ml of dry and pure gasoline (kp. 100-125 ° C) is used as a cooling device presented as about 0.3 molar solution and at about 40 ° C with four times the molar amount of aluminum haloalkyl as about 25% solution in gasoline dropwise while stirring within offset by about 15 minutes. It falls in a strongly exothermic Reaction a dark brown precipitate.

If the titanium or vanadium compound is not a liquid and does not dissolve in the solvent, the solid metal compound is previously brought into solution in the liquid and then made up to 100 ml. If both compounds are solid, the reaction with the organic aluminum compound in Form a finely divided suspension by a fast / running Stirrer carried out. The precipitation of the transition metal compounds with the organic chlorine and / or bromine-containing Aluminum compound can be in the reaction vessel at the same time or be carried out one after the other in a different order.

0 0 9 8 /> S / 1 $ 9 8

BATH ORIGINAL

The reaction mixture is made up to 250 ml with gasoline and can already be used in this form as a catalyst for the polymerization.

Expediently, 25 ml of the fresh catalyst suspension obtained are pipetted into 100 ml of gasoline which contain 4.1 mmol or 7.1 mmol of aluminum haloalkyl. This catalyst suspension is allowed to mature or is heated for a longer time einfacn 1/2 hour at reflux, to about 110 ⁰ C. Thereafter, filled with gasoline - 0.5 g / l organic aluminum compound - to 250 ml. This suspension represents the formed ready-to-use catalyst a (Table I), of which 0.25 mmol of transition metal compound mixture in 1 l of gasoline is used for the polymerization.

If necessary, after the solid catalyst has cooled down and settled by decanting the supernatant liquid several times with gasoline, the 0.5 g / l organic aluminum compound contains, the catalyst has largely been freed from the substances originally dissolved in gasoline, and the washed one Catalyst b (Table I) then - for better metering in the form of a suspension - used for the polymerization.

The variations of the catalysts are shown in Table I.

The catalyst systems listed in Table I are also prepared with compounds of zinc and / or cadmium added. Using the example of aluminum triethyl / zinc chloride, the following illustration and procedure are portrayed.

1. Representation of the additional components

In an apparatus filled with nitrogen, equipped with a stirrer and reflux condenser, 12 g of anhydrous Zinc chloride in 50 ml of gasoline (boiling point 100-125 ° C) presented

BAD ORIGINAL =

009846/1698

and at about 20 ° C. within 1 hour, 50 g of aluminum triethyl added dropwise as an approximately 25% solution in gasoline. (That Molar ratio of aluminum: zinc compound is 5: 1). Heat to complete the reaction then reflux for one hour and filter the cloudy liquid under dry nitrogen. The solution is used directly for the production of catalysts.

Likewise, you can easily zinc diet and anhydrous zinc chloride in equimolar proportions in gasoline Mix the solution, if necessary let it reflux and gradually Use cooling.

2. Use of additional components

The components can be added to the i & catalyzer systems in the following way (Table I) are added:

a) the vanadium or titanium compound or a mixture thereof is placed in a gasoline solution and mixed with aluminum haloalkyl and an additional solution according to 1.) in a molar ratio of 5 '· 1 or a mixture of aluminum haloalkyl and the additional solution is added dropwise. If necessary, the titanium or vanadium compound is added and, after the precipitation, the process continues as described above.

b) is carried out first, as described above, the additive solution is immediately after the precipitation, and the reaction mixture then heated to about 100 ⁰ C.

c) you work first as described and set the additional solution as a cocatalyst to the formed catalyst.

d) work as described and set the additional solution as a cocatalyst for the formed, solid catalyst which has been washed free of all other substances.

009846/1698 bad original

- ίο -

B) polymerization

1. In a 2 l reaction vessel equipped with a stirrer, reflux condenser and thermometer, after intensive nitrogen purging 1 l of pure gasoline mixed with 0.5 g of aluminum alkyl compound is heated to about 40 ° C. and then a prepared according to A) and in Table I listed a catalyst. Ethylene, which was previously cleaned by a petroleum-based aluminum triethyl-containing washing solution, is now introduced. The temperature is maintained between 7 ° and 75 ° C. during the polymerization. After a running time of 3 hours, the uptake of ethylene is almost complete, the precipitated polymer is separated off from the gasoline and dried at 100 ° C. in a drying cabinet
can be seen from Table II.

100 ° C dried in a drying cabinet. The results are

2. In a 2 liter reactor, provided with olefin and hydrogen feed, thermometer connector, manometer, cooling jacket ,. Filling and drainage valve, after flushing the lines and the reactor with nitrogen, 1 liter of gasoline mixed with aluminum alkyl is introduced. After the addition of the catalyst, the reactor is flushed two or three times with hydrogen, the desired hydrogen content is added and the water supply is shut off. Finally, the olefin is continuously introduced during the polymerization up to the desired volume ratio of the two gases to a total pressure of 5 atmospheres. After a reaction time of ^ hours at 70-80 ⁰ C and 5 atm is substantially complete the polymerization. The supply of olefins is stopped, the excess pressure is released and the polymer is removed from the autoclave.

After running off gasoline, the product is dried, weighed, and the physical data are recorded certainly. The results are shown in Table III.

3. 6 1 gasoline, mixed with 1 g / l aluminum alkyl compound, in The catalyst is added to a 10 l pressure reactor. The polymerization of the olefin is carried out by a continuous Add the olefin and hydrogen at total pressure

0 0 9 8 4 6/1698 ^ßÄD original

of 40 atu and a temperature of 75-80 C within Performed 3 hours · The results are in the table IV listed.

BATH ORIGINAL 009846/1698

Table I.

description
of the catalyst

Titanium compound

Vanadium compound

Ratio of Ti / V compound molar

Aluminum connection

A1 / Ti-V compound ratio molar

1 1a

2
2a

3
3a
4th
4a

5a
6th
6a

7a

oa

9a
10
10a
11th

11a

12th

Ti (OnC ₄ H ₉ ) ₄ VO (OnC ₄ H ₉ ) -

It

It

ti it it dd

It It ti ti

ti

Il It W. It H dd dd It it

It It

tt tt tt tt tt

Il ti It It ti It It It It It Il ti

ti Il

1: 3

It

It ti

0.5: 9.5 t

1: 7

Il

1: 4

ti

1: 2

dd

1: 1

It

5: .1

It

8: 1

9.5: 0.5

ti

1: 3

AL (C ₂ H ₅ ) ₂ C1

It

Al (C ₂ H ₅ ) Cl ₂

ti

A1 (C ₂ H ₅ ) ₂ C1

It It Il

dd

ti

Il

dd

It Il

dd

It

dd

ti

dd

Al (C ₂ H ₅ ) Cl ₂

5.5 4th

5.5 4th

5.5

5.5 4th

5.5 4th

5.5 4th

5.5 4th

5.5 4th

5.5

^: 4

5.5 4th

5.5 4th

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

1 1

, α

φ ω>

• Η I SS H-HO: cd EH E

ω H

bfl

• Η fi co, Q

a U λ α>>

φ hO

cd τ3 ■ ρ α • Η -Η EH, Q

Ul

§ CO

O i>j; Η H Φ CU N -P (D α}

1318995

bO OJ H Ö Ü I. O OJ P. T) 3 •H IT ini r » , ^ OJ ε (D OJ O > Ü H < • H Ul CC • Η φ £ j > U ι cd H K \ , —I ■ s •H φ r—

- 15 -

in ■ = * ■ in

in m

in - = J- in in ^ t in in ■ = * · in - = t · m

in in

in in

O O ^

t>>

OJ - = 1-CT> ON

O Ö Ö O

• Η · Η

cn

ON

O O

-P

O -P (D O cd H> s • Ρ (D O CD

-—Ν O

C-cd

O =

«~ Ν O

+> -P cd (D Ö O cd H ί3 P (DO cd

cd οϋΓΛ

τ-τ-

CD

cd i

cd id χι

cdiJ

in

in

PQ

OJ OJ *

-P cd Ü O -P (DO cd H

-P

cd ο

PQ

OJ OJ

OJ

in OJ in oj in · * · »%

(Λ

OJ

PQ

OJ

r-i

OJ

cd HO

cd =

• Η

Eh

PQ

OJ O O

9 8 4 6/1638

cd cd cd cd cd

T-r-T-OJOJOJOJOJ OJ

BATH ORIGINAL

Designation d. Catalyst

Titanium compound

Vanadium compound

relationship : 3 Aluminum- relationship 1 Ti-A-Verb. ti link Al- / Ti-V-conn 1 molar : 2 molar 1 1 Il Al (C ₂ H ₅ ) ₂ C1 4: 1 ti Il 5.5: 1 1 : 3 Al (C ₂ h) ₂ C1 4: 1 Il ti 5.5: 1 Il It 5.5: 1 1 : 2 AlCl ₃ , Al (C ₂ H ₅ ) 3 ^5: 1 It Il 4.5: 1 : 3 Il 4.5 : 1 1 ti Al (C ₂ H ₅ ) Cl ₂ 3 : 1 It ti 4.5 : 1 1 . Al (C ₂ H ₅ J ₂ Br 4th : 1 It ti, ■ 5.5 : 1 ^: 2 It 5.5 : 1 1 It Al (CH) _O C1 4th : 1 : 2 2 ,, 5 2 5.5 : 1 . ■ 1 It AKc ₂ H ₅ ) Br ₂ • 3 : 1 9 3 ' ti 4.5 : 1 1 It A ^ C ₂ H ₅ J ₅ Br ₅ 3 ; . '.? ■', It 4.5 1 Al (C ₂ H ₅ J ₂ Cl 4 ■ 5 ,. 1 'Äl (C ₂ H- ₅ ) ₂ Br ² ^

23 23a 24 24a 24b

25 a ο 25 b S26 "26a cn27 ÜT 27a σ * 27b

Ti

VO (OnC ₂₁ H ₉ )

ti

Il VO (OnC ₂₁ Hg) ₃
It 5 ti Il Ti (O ₂ CC ₅ H ₇ ) I ₊ VO (O ₂ CC ₃ H ₇ ) > 3 dd dd Ti (O ₂ CC ₇ H ₁₅ ) J ₁
It VO (O ₂ CC ₇ H ₁₅
ti Ti (Q ₂ CC ^) ₁₊
Il
It VO (OnC ₄ H ₉ )
Il
It

Ti (OnC ..H ₇ ) ρ (O ₂ GH) _? VO (OnC, H ₇ )

_m ί OnC Ji ₇ ) ρ

_T1

(OnC ₅ H ₇ J

VO (OpCCIU)

28a, 29

29a 30

30a 31 31a 32 32a

+) Tetrakis (hydroxy-exo-dihydro-dicyclopentadlenyl) titanate

Ti (O ₀ CCHpCOp ') ρ ^< -ji ^c; ^^

Ti (O ₂ C (CH ₂ ) ^ CO ₂ )

5.5

OO CD CD

Designation d. Titanium catalyst compound

Vanaüiri connection

Ratio Ti- / V-Verb. molar

Aluminum compound

Al- / Ti-V-Verb ratio, molar

O CO CD

33 33a

34a 35

35a

36a

37a 37b

38a

39a 39b

Ti (OnCJi ₇ ;

dd

Ti

Ti

(OnC ₅ I.

3V2 (O ₂ CCH = CIiCO ₂ )

(OnC ₃ H ₇ ) ₂ (O ₂ CCH ₂ CH ₂ CO ₂ )

(OnC ₄ H _q ) _p

11th

VO (OnC ₄ H _{9 y}

T ¹ (O ₂ CChIcHCO ₂ IC ₃ H ₇ J ₃ VO (OiC ₃ H ₇ ) _?

^T1

(OnC, H _Q ) _p

(O ₂ CCH ₂ CH ₂ CO ₂ nC ₄ H η

(OnC ₄ H) ₂

dd dd

1: 1

1: 2

It

1: 3

1: 3

1: 3

Al (ibu) _o Cl

: 3

1: 3

It

It

Al (IBu) ₀ Cl

dd

'2 ^X

Al (iProp) ₂ Br

dd

Al (OC ₂ H ₅ J ₂ Cl,
Al (C ₂ H ₅ J ₃

Al (C ₂ H ₅ ) Br ₂

AlBr

4th
5.5

5
6.5

5.5 4th

5.5

6.5
6.5

5.5

5.5 5.5

1 1 1 1 1

1 1

1 1

1 1

1 1

1 1

OO CD CD

Table II (polymerization / pressureless) ethylene

Designation d, yield Designation d. Catalyst g / l solvent / 3h catalyst yield designation d.
g / l solvent / 3h catalyst

Yield g / l of solution / 3h

cn
<o
ct>

1 1a 2 2a 3 3a 4 4a 5 5a 6 6a

9a 10 10a 11 11a 12 12a 13 13a 14 14a.

33 15th 154 15a 51 16 170 16a 16b 66 " 17th 17a ö6 17b 35 18th 18a 48 18b 125 19th 32 19a 98 20th 20a 58 21 21a 49 22nd 22a 22nd 23 23a 8th 24 24a 142 24b 68 '25 126 25a 72 25b 113 20th 26a

68
145
135
223
220

69
125
118
165
219
215

22nd
190

173

240

32
210

62

137

30th

150

48

165

135

163

168

151

59
212

27

27a

27b

2ö

28a

29
29a

30 ·
30a

31
31a

32
32a

33
33a

34
34a

35

³ nights
36

36a

37

37a

37b

³ §
38a

39

39a

39b

112

173 162 110

208

15 92 98

163 53

108 62

118 22

67 46 98 53 95 55 163

& 180

172 162 212

197

223

231

00 CO CO

691/9 ^ 8600

IH

IB

ro to ro ro ro ro ro ro ro to ro ro ro ro v & ro - * - *

CO 00-5 -3 -5 OUl Ul Ul 4 = · 4 = \ jJ Γ0 - * OO νοθΟΟ PD "P ρ Kf p Cf PP ί> PPPO ¹ P

43σ <ΛΟ> ^ 4? ^ ΓΟ D * J »O ⁴ P Ρ Ρ Ρ p

P Ui ro - * PPP

UI - * - * - * - * - »-» · * - * - χ -λ _α OO Ul ΟΟΟΟΟΟΟΟΟΟ OOOOUiUlUlUlUiUlOOOOO OO OO OOOO OO ΟΟΟΟΟΟΟΟΟΟΟΟΟΟΟΟ ΟΟΟΟΟ ΟΟΟΟ ΟΟΟΟΟΟΟ O

roro- ^ rororororororororororororo- ¹ - ^ - »-'-» ^ rororororo rorororo ro ro ro ro

VJiVJi Ul Ul Ul O O OUiUiUiUiUlUlUiUiUiUiUlUiUiUiUiUlUlUlUIUiUi UIUiUiUl Ui UiUl Ul OOUI-3 -AVjJ OO00O \ U1 -JJ CO- ¹ COVO OC IO CO-AOΓ0-3VOOOCTVjJ Γ0- »VO-» VjJ 4 = -ON ON

4 ^ on on ro ro VjJ oavjjui ooon- < rov> j o> o> ^ oooonvjjonvjioui co onooocvovjjoo- ^ vo

OO VD O OC ^ OO - * U1 OVO OOOVO O COO -trOOVOVOVJlVOOOOOCOUI COONVjJ- * to 4VjJ 4
_1VD VJIVjJVO Pu On OOΓΟVjJ VJl OnOOCCVjJ OO On- «3 00 4 = -00-» VOVOVjJUlONrO COUlVOrO CO- ^ VjJ ΓΟ

-Li-

'Name of the catalyst 36a .Copolymerization: ^ί Use UM ¹ partial pressure 0 yield ( V red value 2.01 · 1 te -. 37a Name of the catalyst mg / 1 H ₂ g / l solvent / 3h 1.25 CO OO 37b 100 2.5 121 1.59 I. CO
CO 38 Ethylea / propylene 9 °: 10 18a 100 2.5 162 1.88 1.36 cn 38a Xthjlen ^ Büten-1 90:10 I8a 100 2.5 151 1.98 39 50 1.5 133 2.12 39a ifSSSSrl 90 s'iViöa 50 1.5 198 2.32 :. 39b 100 2.5 173 1.61 Name of the catalyst 70 1.5 200 2.03 70 1.5 211 2, 18 Propylene I6b Use of ÜM ^S Yield**) red-? value "" "■ 20a mg / 1 'Partial pressure g / l solvent / 3h O
O 39b 100 2 12.1 AROUND te ^ U-Butglen 16b 50 0.25 3.5 P.
H· . -. ". , _20a 70 0.25 14.8 3.8 O 39b 100 8.8 Ct 4 "methylpentene-1 16b
.——— 11.6—., _20a 50 7.8 1.4 CR
(D 39b 70 11.2 3
(D 0> 100
50 Solvent 5.3
8.2 cn
ω
(D 70 5.6 ►- * Use UM * Yield * ' \ A ^ red value mg / 1 g / l solvent / 3h g / mg V 3h 50 176 70 263 ' 70 96 ϋξ) UM s transition metal compound feift) 'total polymer after driving off the
./ ■ ■ '■ ■ ι
I.
I.

Me) UM »transition metal compound

Table IV Polymerization at 40 atmospheric pressure
Ethjrlen

Designation d. Use UM * 'partial pressure. ·. ucbeut u ν

Catalyst nig / 1 H _{2 (j} / l Lüsun ,, sin. / 3h t, -7 »" £ ¹ ^

1a 20 , 24 120

2a 20 24 132

5a 20 24 122

12a 20 24 119

14a 20 24 120

16 20 24 177

16a 20 24 1üö

ο 16b 20 24 172

■ O 18a 5 12 200 '

■ £ ■. . 18b 5 12 165

£ 19a 5. 12 178

m 20a 5 12 143

«S 21a '5 12 148 ■ 9,,

- 24a 20 24 132 66 165 '

<» 24b 20 24 122 6.1 1.52 r ± ..

«O 25 20 24 217 '109 181

° * 25b 20 24. 217

26b 20 24 204-

30a 5 12 172

37a 20 24 185

38a 5 12 155

39 5 12 182

39a 5 12 198

39b 5 12 2o1

b, 0 1.39 5.6 1.85 6.1 1.29 $, 9 1.70 6.0 1.25 8 / ö t58 9.4 1.12 8.6 1.68 40.0 3.08 32.0 2.90 35.6 2.51 28.6 2.43 29.6 2.00 6.6 1.65 6.1 1.52 10.9 1.81 10.9 1.69 10.2 1.91 34.4 1.93 9.3 1.58 32.0 2.86 36.4 2.57 39, ö 2.20 40.0 2.98

OO CD CO

Portion Table IV Polymerization at 40 atmospheric pressure

Bez.d. Additions to the Al- / Zu- ^W Al- / Zn- or. ' Use uM' h cat. used cataly- conn. Cd-connection ni ^ / 1 It.Tab.I satorsystem (molar) (molar)

1a

2a

1a

18a

18a 18a 18a

Al (C ₂ H ₅ ) ,, ZnCl ₂ Verf.n. A) 2a) Al (C ₂ II ₅ ) ,, ZnBr ₂ Verf.n. a) 2b) ZnCl ₂ , Zn (C ₂ H ₅ ) ₂ Verf.nA) 2c) Al (CgH ₅ J ₂ Cl, Zn- (C ₂ H ₅ J ₂ * Verf.n. A) 2a)

Zn (C ₂ H ₅ ) ₂ method according to A) 2c) ZnCl ₂ , Cd (C ₂ H ₅ ) ₂ method η. Λ) 2d) Cd (c ₂ ii ₅ ) ₂ author. N. A) 2b)

10.5:

8.5:

5.5:

8.5:

5.5:

5.5:

5.5:

tip yield
g / l LSM / 3h g / mg ÜrVj 28.6 1.01 12th 142 29, ö 1.25 12th 14b 26.6 0.85 12th 133 40.5 1.34 12th 212 37.6 0.88 ι 12th , 83

233

198

46.6
39.6

1.05

*) in the additional solution c)

in the catalytic converter

UM = transition metal bond CD __v

Claims (6)

1.) Process for the polymerization of qC -olefins and; mixtures thereof with 2-6 carbon atoms, characterized in that, to carry out the polymerization, catalysts composed of, on the one hand, mixtures of halogen-free organic titanium and vanadium compounds and, on the other hand, one or more chlorine- and / or bromine-containing organometallic compounds of I. to III. Group of the Periodic Table, optionally with the addition of aluminum trialkyls and / or zinc and / or cadminum dialkyls. 2.) The method according to claim 1, characterized in that as organic titanium or vanadium compound enolate ,. Acylate, Compounds containing phenolate, alkoxyl groups or mixtures thereof can be used. 2>) Process according to claim 1, characterized in that, as organometallic compounds aluminum compounds are used. 4 ·.) Method according to one or more of the preceding claims, characterized in that in addition to the organic titanium and Vanadium compounds are used from which compounds the organometallic compounds mentioned arise in situ. 5 ») Method according to claims 1 - 4> characterized in that the metanorganic compounds in the precipitation of the Transition metal connection parts are added. 6.) Process according to claims 1 - 4, characterized in that that the organometallic compounds after the precipitation and optionally after the catalyst has been formed and washed freshly added. 00 984 6/16 98