DE1099168B - Process for the polymerisation of olefins or olefin-containing gases - Google Patents

Description

Patent 1,064,718 protects a process according to which the polymerization of olefins or olefin-containing gases by means of catalyst combinations containing organometallic compounds According to Ziegler, high polymers are also possible without the presence of inert, organic auxiliary liquids is. This is done in two stages. In a first stage, a small part of the polymer is in an inert, organic auxiliary liquid and in the second stage after reducing the amount of auxiliary liquid further polymerized. The method is characterized in that as an auxiliary liquid an inert, low-boiling organic one, preferably boiling below the reaction temperature Liquid or a mixture of such liquids used and after formation of the polymer of first stage is practically completely removed by evaporation. Because by the reaction that led to the formation leads to fresh polymer, catalyst is consumed, the reaction would come to a standstill, unless further catalyst is added during the reaction.

According to the patent, one leads to maintain the polymerization when the effectiveness of the catalyst complex decreases, the catalyst components that form the active catalyst complex, unmixed in concentrated form or in dilute form by dissolving in a low-boiling solvent Form or else clogs the catalyst complex formed from the components as a whole.

These types of further addition of the catalyst components or the catalyst complex show however, it has certain shortcomings. Since the second stage of the process worked without a diluent is not a uniform concentration due to the addition of catalyst at certain time intervals the catalyst complex guaranteed in the reaction mixture. The desired even concentration of the catalyst complex during the polymerization is particularly difficult if one works with very small amounts of catalyst and wants to add them discontinuously. This is also true, when the catalyst components or the catalyst complex with the aid of inert, organic Solvents are added to the reaction chamber in liquid form that can be dripped.

It has now been found that in the second stage of the process, after the practically complete removal of the low-boiling organic liquid, the catalyst components can be introduced into the reaction vessel in vapor or gas or mist form as pure substances or diluted with a solvent, and the process continues Catalyze the reaction just as if it were directly in the drip polymerisation process
of olefins or olefin-containing gases

Addendum to patent 1,064,718

Applicant:

Gelsenberg Gasoline Corporation,
Gelsenkirchen-Horst

Dr. Herbert Frieß, Gladbeck,
has been named as the inventor

in liquid form or in dilute, drip liquid form with the aid of a liquid solvent or diluent would have been entered into the reaction chamber.

In the second stage of the process z. B. in an ongoing dry polymerization with Introduced the catalyst components using a carrier gas.

The advantages of the method according to the invention consist in a constant and uniform contact addition into the reaction space against the uneven and periodic supply of the catalyst components, in which these are mixed directly without a solvent or diluent or with a Solvents or thinners can be supplied. Also in relation to the subsequent delivery of the contact in the presence of liquid solvents, the claimed process has the advantage that the introduction the liquid used in the catalyst does not have to be removed again afterwards.

example 1

According to Example 1 of the patent specification 1,064,718, dry polymerization was carried out in the following manner Gear brought: 1000 ml of pure η-hexane were placed in a reaction vessel and passed through pure ethylene intensively stirred. After one hour, 3 ml of aluminum triethyl and 1 ml of titanium tetrachloride were added admitted. Immediately thereafter, the polymerization began, with the temperature rising rapidly 65 ° C rose and the solvent was distilled off with the gas stream. By recycling the condensed The distillate was processed in such a way that about 50 to 100 g of polymer were formed, whereupon the solution

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medium was no longer returned. Then ethylene was passed in with vigorous stirring, wherein the heat of reaction that occurs removes the remainder of the solvent from the reaction vessel by distillation removed. Through these measures, a dry polymerization was achieved, which after a running time 17 hours was on the decline.

In order to revive the polymerization, there was further contact, but now in vapor form, the Reaction space supplied. A fritted wash bottle with titanium tetrachloride was kept at 20 ° C. A stream of 21 ethylene per hour was passed through it. Another wash bottle with a frit with aluminum triethyl was kept at 124 ° C. Likewise a stream of 21 ethylene per hour was passed through it. The two with the catalyst fumes Loaded ethylene streams combined in the reaction space. At the same time and from these with the Separate partial streams laden with catalyst vapors, pure ethylene was introduced into the reaction chamber. The uptake of ethylene increased from 20 to 110 l / hour. The reaction was so violent that the temperature rose to 70 ° C, so that cooling had to be carried out. After IV2 hours the attempt was canceled. A total of 1500 g of polymer were obtained in this experiment.

Example 2

As explained in Example 1, after the polymerization in η-hexane in the first process stage and after removal of the diluent, a dry polymerization is carried out in the second stage, which had subsided after a running time of 3 hours. To restart the polymerization energize, further contact, but now in vapor form, was introduced into the reaction chamber. One Wash bottle with frit with titanium tetrachloride was kept at 20 ° C and a flow of 11 nitrogen each 5 'hour passed. Another wash bottle with a frit with aluminum triethyl was at 90 ° C held and passed a stream of 10 1 nitrogen per hour. The two with the catalyst fumes Loaded ethylene streams combined in the reaction space. At the same time, but from these with the partial streams loaded with the catalyst vapors separated, pure ethylene was in the reaction space initiated. The uptake of ethylene then rose from 0 to 80 l / hour. The reaction went like this violent that the temperature rose to 80 ° C, at times even to 90 ° C and are cooled again and again had to. The experiment was terminated after 8 hours. The yield was 1575 g.

With this type of contact addition, the polymerization can be kept running for as long as desired.

Claims (1)

Claim: Process for the polymerization of olefins or olefin-containing gases according to patent 1,064,718, thereby characterized in that in the second stage of the process after the practically complete removal the low-boiling organic liquid, the separate replenishment of the catalyst components takes place alone or as solutions in vapor, gas or mist form. Legacy Patents Considered:
German Patent No. 1 000601.