DE1770240C3 - Process for the polymerization of ethylene - Google Patents

Description

2. The method according to claim 1, characterized in that

draws that a catalyst is used in the production of component (A) an aluminum

to produce the component (A as (1) ™ '" ^e ^ 3 compound of the formula AlR ₂ X,

Titanium (lV) compound titanium tetrachloride and / or mumorgin ^ he verb nd ^ g ^ ^ ^.

use a titanium acid tetraester. 35 wob. K en, en halogen atom,

3. The method according to claim 1 and 2, characterized S'ni Alkoxv or Mercaptogruppc or characterized in that a catalyst emgesetz ^^ fo'Mom means, has been used, in which for the preparation of component (A) Wassersto taiom dlucui, _b

_i0 (2) the concentration of component (A) 0.1 to

(3) the concentration of component (B) 10 to

100 mg / 1 and

(4) the ethylene partial pressure is 3 to 60 kgf / cm ² .

• ι Aic titanium connections are in particular titanium

It is already known that conversion mixtures from Als Htan (iyj verDinumib

^ss

lead that from a catalyst claimed by reduction of a mixture orkonzei tra cal of TiCl ₁ and VOCl, with an aluminum tri- approximately the following low. Kata alkyl, optionally in a BF ₃ atmosphere, obtained

shear connection is about 6 e / ks Polyäthylcii. probably hmsic itl.cli der

^ trXriL'f- "S ΙΤ n _U , ₈ e-

3 4

Very small amounts of organometallic compound and that with a partial water pressure of 4.8 ata

Transition metal compound used. The cat-regulated melt index /, (according to ASTM D 1238) der

Nevertheless, the analyzer shows a high level of activity; the resulting polymer was about 21 in both cases.

Polymers contain only extremely little catalysts. The consumption of heavy metal compounds could

Satorreste, a follow-up treatment to remove the 5, i.e. by reducing the concentration of the mctali-

Catalysts from the polymer is not required- organic component from 1000 mg / 1 to 50 mg / 1

Huh Reduced by 45% if all processing measures are no longer required. The consumption of triethyl

minimal amounts of catalyst residues result. aluminum was only about 3% of in Example 1

When compared to the comparison experiment, the polymerization products show

processing an increased aging resistance as well as io

good color stability. In the processing measures B e i s η i e 1 2 machines does not corrode, so common

Additives to prevent corrosion, such as B. CaI- With the catalyst described in Example 1, cium stearate, which often give rise to disturbances, ethylene could be generated in partial traps in the same apparatus. i ₅ pressures of 13.0 ata ethylene and 22 ata hydrogen

Another advantage can be seen in the fact that it polymerizes.

due to less use of the expensive aluminum alkyl- The catalyst concentration was: Connections can be worked more economically.

In the process according to the invention, 6 mg / 1 transition metal compounds,

Regulation of the molecular weight for Ziegler polymer 20 30 mg / 1 triethylaluminum. Sations usual means are used, such. B.

Hydrogen or zinc alkyl compounds. There were 1501 / h. Catalyst suspension

As a diluent, the inert liquids known for this purpose at a liquid level of 300 l in the stirred tank, such as. B. aliphatic, are used. Thus, in the 15th and 16th hours of the cycloaliphatic and aromatic hydrochloric acid experiment, 49.0 kg of polyethylene with a melting substance were used. index Z ₅ of 10 (ASTM D 1238) obtained.

_R. · Ιι This corresponds to a catalyst consumption of:

and comparative _{experiment 36 mg} heavy metal compounds _and

The catalyst used for the polymerization 30 180 mg of triethylaluminum per kg of polyethylene, was prepared as follows: 1 mole of n-propyl titanate and

3 mol of vanadium oxychloride were mixed in 3.5 1 of heptane. The ash content in the polymer was 40 parts each

thinned and then refluxed for 2 hours million parts,

cooks. After the mixture had cooled, 8 moles of B e i s o i e 1 3

Diethyl aluminum chloride dissolved in 51 heptane at 35

approx. 30 ° C slowly added over 2 hours. The precipitate formed in a reduction process similar to that in Example 2 was filtered from ethylene partial pressure of 18.2 ata and water, washed and resuspended. The partial pressure of 16.8 ata with the suspension retained above was polymerized after the addition of triethyl-written catalyst, and aluminum was used for the polymerization. 40 The following catalyst concentrations were used in a jacket-cooled stirred tank:
continuous 100 1 / h of the diluted with hexane

Pumped catalyst mixture. The liquid level 1 mg / 1 transition metal compounds,

in a container of 100 1 was 50 mg / 1 triethylaluminum with a Co-60 emitter.

regulated. The polymer leaving the container 45

suspension was in a subsequent stirring In the 15th and 16th hours were thus 19.8 kg

relaxed container and from there to a centrifuge made of polyethylene with a melt index / _ä of 1.4

given. The centrifuge-moist powder was then put

dried at about 8O ⁰ C in vacuo. This results in a catalyst consumption of:

At a concentration of 17.5 mg / 1 of the above-mentioned 50

wrote transition metal compound mixture 15 mg transition metal compounds and

and a) 1000 mg / 1 (comparative test) or b) 50 mg / 1 760 mg triethylaluminum per kg of polyethylene. (Example 1) Triethylaluminum became ethylene at

an ethylene partial pressure of 3.2 ata polymerized. The ash content in the polymer was 100 parts

The yield in the comparative experiment was 10.0 kg 55 per million parts.

Polyethylene / hour and in example 1 18.6 kg poly- example 4 ethylene / hour

This corresponds to a catalyst consumption of: To produce the catalyst, 5.6 moles of diiso-

butylaluminum fluoride presented in 14 l of heptane. Here-

Comparative _{experiment (io to wur (k a} mixture of 1.6 mol of titanium tetrachloride

175 mg of transition metal compounds according Po kg and 2.4 mol Vanadinoxychlorid at -30 ⁰ C hinzu-

ethylene and dosed. The precipitate precipitated out was

9980 mg of triethylaluminum per kg of polyethylene; filtered off, washed and then resuspended.

. , This suspension was then used as a catalyst component

Example 1 game 1 _{6s not} used.

94 mg of transition metal compounds per kg of Po- For polymerization at an ethylene partial pressure

ethylene and of 22 ata with the addition of 6% by weight of butylene, bc-

270 mg of triethylaluminum per kg of polyethylene. drew on ethylene, and a partial pressure of hydrogen

of 11.5 ata in the apparatus described in Example 1, a concentration of 0.07 mg / l of the catalyst component described above was used. Triulhylaluminum in a concentration of 50 mg / l was used as the organometallic component. This means that in 2.1. In the 22nd and 22nd hours of the experiment, 17.3 kg of polyethylene with a melting index / _B of 2.1 (ASTM D 1238) were obtained.
This results in a catalyst consumption of: 11.5 mg of transition metal compounds and
870.0 mg triulrylaluminum per kg polyethylene.

The ash content in the polymer was 70 parts each, if no catalyst washes off Million parts.

Example 5

With the catalyst described in Example 1, ethylene was at an Älhylcnparliuldruck of 35 ata polymerized in the absence of hydrogen. The catalyst concentrations were:

0.2 mg / l transition metal compound mixture, 50! O mg / l triethylaluminum.

ίο This was in the 9th and 10th hours of the attempt 39.6 kg / polyethylene received.

This corresponds to a catalyst consumption of:

1.5 mg of transition metal compounds and 38o 'mg of triethylaluminum per kg of polyethylene.

Claims (1)

Z. ■; 1 Olefins, the catalyst concentration, in particular the amounts of T.lan-Va.uidin compound to be used, is reduced even further. x "ι, the polymer produced by this process! - ■ 1. Process for the polymerization of ethylene, _cnUia | but still _len an unwanted, if appropriate, suspended in a mixture with other vOlclinen, 5 ^ ^ negligible Aluminiumgcliiih ,: ■ using _isl agents in inert Vcrdunnungs- _{at dcr} preparation of the polymers partially or covet catalysts ι ei _{'td sc} | _iw icrig to handle Borlriaus (A) reduction products of mixtures of d J ^ ^cn ^ _cr , _i , Titanium (IV) and vanadium (V) compounds with " ^U £""J _{dc have now} surprisingly found that; organoaluminum compounds and (H) aluminum - _the polymerization of olelines using organomine and / or organozinc Ver °. . Press the organic component bindings, characterized mim ^^ ^ ^ can be lowered, rather that there _{is still} a reduction in catalyst consumption _{(1) an aluminum consumption is} achieved for the production of component (A). When lowering the concenminium organic compound of the formula ⁵ ■ _the organometallic component of 1000 rag / 1 to 50 mg / 1, the catalyst consumption AlR ₂ X fell _by 45 '/ It was not to be expected that with this aeringen 'concentration of inorganic grain where R is a hydrocarbon _radical with a ^ ° onente still a polymerization instead of carbon atoms from 2 to 6 and X is a halogen line _(jet atom, an alkoxy or mercapto group. The invention therefore relates to a process or means a hydrogen atom, used polymerization of ethylene, optionally im and that mixture with other .x oils, using (2) the concentration of component (A) 0.1 to. _inert diluents suspended or 25 mg / 1, _tnw . ⁵ dissolved catalysts from (A) reduction products (3) the concentration of component (B) 10 to ^ _{n mixtures} of titanium (IV) and vanadium (V) ver-100 mg / l and bonds with organoaluminum compounds (4) the Ätliylenparlialdruck 3 to 60 kp / cm-, _{(ß) alum} i _n i _U morganischen and / or zinkorganisittrs. 3o see connections, which is characterized by