DE1268846B - Process for the production of polyolefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German KL: 39 c- 25/01

Number: 1268 846

File number: P 12 68 846.9-44

Filing date: June 16, 1955

Open date: May 22, 1968

It is known to use ethylene with a mixture of aluminum chloride and titanium (4) chloride, if appropriate to polymerize with the addition of hydrochloric acid binding metals. In addition to solid Polyethylene liquid to soft wax-like products.

Furthermore, US Pat. No. 2,691,647 discloses a process for the polymerization of ethylene and Propylene in the presence of an oxide of a metal of VI. Subgroup of the periodic table and one Alkali metal known. However, this method has the disadvantage that the rate of polymerization is low and that the polymer formed can be detached from the contact carrier in the heat and the polymer solution obtained then has to be filtered.

It has now been found that olefinic hydrocarbons can be given a special one below The initiator system set out above while avoiding the disadvantages of US Pat. No. 2,691,647 can implement high molecular weight, film-forming substances with excellent mechanical properties.

The invention relates to a process for the preparation of polyolefins by polymerizing olefin hydrocarbons with the aid of catalysts composed of (1) metals which bind hydrochloric acid and (2) metal compounds, which is characterized in that polymerisation is carried out in the absence of aluminum halides and the metal compounds are those of the general formula MeX _7n or MeO _n Y ₃ ,, in which: Me stands for mercury or a metal of subgroups I or IV to VII - with the exception of titanium - or of group VIII of the Periodic Table of the Elements; O for oxygen; X for halogen, —CN, —SCN ₅ —OR, —SR or

- OCOR; Y for halogen, —OR, —SR or

- OCOR, where R is an alkyl radical and m, η and ρ are numbers that result from the valency of the metal, is used; with the exception of a process for the polymerization of ethylene using a mixture of

a) at least one of the free metals sodium, potassium, lithium, rubidium, cesium, beryllium, Magnesium, zinc, cadmium, mercury, gallium, indium, aluminum or thallium and

b) a tri- or tetrahalide of zirconium or hafnium.

_m As olefin hydrocarbons, especially ethylene, propylene or the butylenes and their mixtures with one another come into question, also diolefins, ζ. B. butadiene or isoprene, and vinyl hydrocarbons such as styrene.

Process for the production of polyolefins

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, 67000 Ludwigshafen

Named as inventor:

Dr. Karl Wisseroth, 6700 Ludwigshafen;

Dr. Ernst-Günther Kastning, 6701 Assenheim;

Dr. Herbert Friedrich,

Dr. Hans Albers, 6700 Ludwigshafen

In the above formulas MeX _m
are suitable metals from I. or IV. to VTI. Subgroup or the VIII. Subgroup 2. B. iron, cobalt, nickel, chromium, molybdenum, tungsten, vanadium, zirconium, copper or silver.

Particularly suitable metals binding hydrochloric acid are, for. B. those of the I. main group, such as lithium, Sodium or potassium, the II. Main group, such as magnesium or calcium, also aluminum, zinc, Cadmium or iron. Mixtures or alloys of these metals with one another or their amalgams are used.

The metals are expediently used in powder form and particularly advantageously in colloidal dispersion at. For example, they can be activated with iodine.

The solid metal compounds are also expediently used in a finely powdered and anhydrous form.

The ratio of metal] to metal compound can vary within wide limits. For example the components can be used in equivalent amounts, but both the metal compound as well as the metal must be present in excess.

On the initiator mixture, which is expediently in an organic liquid, e.g. B. an aliphatic cycloaliphatic or aromatic hydrocarbon, dissolved or suspended, is allowed, in particular with the exclusion of oxygen and water, an olefin act. One can under normal pressure polymerize, but expediently uses increased pressure to increase the reaction rate, z. B. Pressures above 20 to 300 at. The reaction temperature is advantageously between 20 and 200 ° C, but under certain circumstances you can also use

809 550/466

Polymerize temperatures down to the boiling point of ethylene (-104 ⁰ C) and up to 300 ° C. The purification of the polymers from inorganic substances can, for. B. be made by washing with dilute, aqueous mineral acids, dilute acetic acid or particularly advantageously with methanolic hydrochloric acid.

The polymers have excellent mechanical properties, e.g. B. high tensile strength, stability and a high melting point. The process can be either discontinuous or continuous are executed.

The parts mentioned in the examples are parts by weight.

For example

10 parts of finely divided sodium, 25 parts of vanadium (5) chloride and 500 parts of xylene are brought into one High pressure shaking autoclave. Then you pass in at 120 ° C ethylene under 200 atm pressure and hold the Pressure by injecting more ethylene with 250 atmospheres. After 15 hours, 405 parts of solid, viscous are obtained Polymer with a melting range of 135 to 140 ° C.

Example2

10 parts of zinc dust which has been treated with hydrogen, 25 parts of chromyl chloride (CrO ₂ Cl ₂ ) and 500 parts of cyclohexane are placed in a high-pressure shaking autoclave. The atmospheric oxygen is displaced with nitrogen and ethylene is then allowed to act at 200 ° C. under 100 atm. Pressure for 15 hours. 82 parts of solid, viscous polymer with a melting range of 135 to 140 ° C. are obtained.

Example 3

35

To a mixture of 10 parts of aluminum powder activated with iodine, 25 parts of chromyl chloride and 600 Parts of cyclohexane, which is in a high pressure shaking autoclave under nitrogen, are left act at 200 ° C for 15 hours ethylene under 200 atm pressure. There will be 80 parts of a solid and tough polymer with a melting range of 135 to 140 ° C.

Example 4

45

Under the conditions mentioned in Example 3, ethylene is polymerized with 10 parts of a finely pulverized, Alloy of 60 parts of magnesium and 40 parts suspended in 600 parts of cyclohexane Aluminum and 25 parts of chromyl chloride as initiator. 150 parts of a solid and tough polymer are obtained from a melting range of 135 to 140 ° C.

Example 5

10 parts of finely divided sodium and 30 parts of anhydrous, freshly sublimed and finely ground iron (3) chloride are placed together with 500 parts of xylene in a high-pressure shaking autoclave under nitrogen. Then allowed to act at 200 ⁰ C ethylene under 200 atm pressure for 12 hours. There are obtained 55 parts of solid, viscous polyethylene having a melting range from 135 to 14O ⁰ C.

Example 6

Ethylene is polymerized under the conditions described in Example 5 with 10 parts of finely divided sodium and 30 parts of copper (2) chloride in 500 parts of xylene. This gives 35 parts of a solid and tough polymer with a melting range of 135 to 140 ^° C.

B e i s ρ i e I 7

10 parts of finely divided sodium and 25 parts of vanadium (5) chloride are placed in a high-pressure shaking autoclave with 500 parts of benzene. Propylene is then passed in at under 30 atm and heated to 100 ° C. under 30 atm propylene pressure for hours. 65 parts of hard wax-like polypropylene with a melting range of 105 to HO ⁰ C are obtained.

Example 8

20 parts of aluminum powder and 40 parts of vanadium tetra-chloride are added to 500 parts of hexane in a high-pressure shaking autoclave. Then it is pressed ethylene at 130 ⁰ C and 200 at a pressure. The ethylene consumed is continuously replenished for 12 hours.

After cooling, 1320 parts of hard, film-forming polyethylene are obtained.

Example 9

500 parts of hexane, 20 parts of sodium powder and 40 parts of anhydrous chromium (3) chloride are introduced into a high-pressure autoclave. Is allowed on this mixture at 160 ⁰ C ethylene under 200 atm pressure hours act. 120 parts of hard, yellowish-colored polyethylene are obtained.

Claims (1)

Claim: Process for the production of polyolefins by polymerizing olefin hydrocarbons with the aid of catalysts of (1) hydrochloric acid-binding metals and (2) metal compounds, characterized in that polymerizing is carried out in the absence of aluminum halides and, as metal compounds, are those of the general formula MeX _OT or MeOJiYp, in which is : Me for mercury or a metal of the I. or IV. To VII. Subgroup - with the exception of titanium - or the VIIL group of the Periodic Table of the Elements; O for oxygen; X for halogen, - CN, - SCN, - OR, —SR or - OCOR; Y for halogen, - OR, —SR or —OCOR, where R is an alkyl radical and m, η and ρ are numbers resulting from the valency of the metal; with the exception of a process for the polymerization of ethylene using a mixture of a) at least one of the free metals sodium, potassium, lithium, rubidium, cesium, beryllium, Magnesium, zinc, cadmium, mercury, gallium, indium, aluminum or thallium and b) a tri- or tetrahalide of zirconium or hafnium. Documents considered: German Patent No. 874 215; U.S. Patent No. 2,691,647. 809 550/466 5.68 © Bundesdruckerei Berlin