DE1292384B - Process for the production of polyethylene - Google Patents

Description

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The subject of the earlier patent 1080 303 is a sufficiently high molecular weight - as a plastic process for the polymerization of ethylene, in which ^: '· For various purposes, in the presence of titanium dichloride or one of these. In the processes according to the earlier patents

containing preformed reaction mixture, 973,626, 1004810 and 1012460 to low pressure Reduction of titanium tetrachloride to titanium di-5 polymers of ethylene are catalysts verchloridstufe by means of aluminum or titanium in the turns, which by reducing certain heavy heat is available in a known manner, polymerized metal compounds by aluminum alkyls or will. Aluminum alkyl halides, i.e. organometallic

In further processing of the compounds related to this patent, while the basic idea of the invention was now found, it was found that even zirconium compounds, in set catalysts the metals aluminum and the zirconium have a valence lower than 4 I titanium , have been used as a reducing agent, and which have been produced by the reduction of zirconium tetra- Compared to the earlier patent 1255 316 hypohalides by means of aluminum or titanium, the process of the invention differs through those who are able to polymerize of the 15 reethylene used to produce the catalysts. "" · reducing agents aluminum and titanium. Aluminum is expressly excluded from this finding as the basis for the erfipr in patent 1255 316; Proper process for the production of poly- Also in the earlier patent 1226 306, the ethylene is produced by polymerizing ethylene in water using catalysts, which are produced from compounds by using free, liquid suspending agents in the presence of aluminum or titanium as reducing agents of metals that have been provided, not claimed. IV. Subgroup of the Periodic System that there,. ..1 ·, is characterized in that a.!; ::., ... Be rs ρ i: e 1: 1. Zirconium compound in which the zirconium has a lower 2 g of zirconium tetrachloride with 2.5 g of aluminum valence than 4 and the 25 nium powder mixed by reduction and heated in a sealed tube of zirconium tetrahalides using aluminum or 8 hours at 200 ° C ₁ . The black to brown titanium has been produced, is used, and the tube content was then suspended with 250 ecm of petroleum ether, if necessary with the addition of activated titanium, and low-grade titanium compounds or Friedel at 50 ° C. ^{in a 3/4-liter V2A stirred autoclave} with ethylene under a pressure of .60 atm Crafts catalysts. 30 treated. After some time, the pressure was

predominantly solid polymers of ethylene-see gas space and liquid had confessed: When

are, arise under, .dem.Influence of the according to the heating to 100 ° C continued the polymerization

Process of the invention used zirconium compound "*" pressure drop and was also waxy polymers through constant ^ re-fertilization. 35 pressing of ethylene and slow temperature rises - kept going by the process according to the present invention to 150 ° C. After 7 hours of manure, therefore, the gap between the after about 170 g of ethylene had been implemented. The process of the patent 1080 303 resulting solid polymers removed from the autoclave after cooling and the crumbly crumbly mass formed in the presence of aluminum chloride was separated from the solvent nium chloride and similar catalysts by suction and closed by treatment with high-boiling oils. concentrated hydrochloric acid and methanol to a large extent. ,from. freed the inorganic constituents. Available polymers can in their own loot 120 g of a viscous resin, which can be modified in hot xylene shafts if the low-value zirconium compound used as a catalyst and cleaned by falling over with methanol could be obtained. As a by-product, activated titanium or low-grade titanium / petroleum ether solution 16 ecm of a hydrocarbon bond or Friedel-Crafts catalysts were added from the manure. mixture of bp _15mm 69 to 15O ⁰ C by distillation

Separated as catalytically effective low-grade zirconium distortion, bond comes in particular zirconium dichloride in .-. Example 2

Question how it can be achieved by reducing zirconium tetra- 50 ""

chloride with titanium or aluminum is obtained. 14.5 g of zirconium tetrachloride were mixed with 3 g of titanium

Instead of pure zirconium-2-chloride, the powder can also be heated to 300 ° C in a closed tube the reduction of zirconium tetrahalide by means of a - after 8 hours the violet to brown reaction of the mentioned methods obtained reaction? - mixture with, 250 ecm benzene in the autoclave suspension mixture be used as catalysts. 55 dated. After saturation with ethylene at 50 ° C and

In order to carry out the air conditioning according to the invention, the polymerization was increased by heating driving to gaseous ethylene in a suspension, .. 150 ° C brought into motion. We were there in 6 hours of the catalyst or catalyst mixture in the "about 170 g of ethylene. The after the diluent The contents of the autoclave, which had largely solidified at room temperature or cold, were increased to a higher temperature, preferably below an increased temperature, by treatment with concentrated hydrochloric acid Pressure to be initiated. The resulting catalyst was and as largely freed as possible Ethylene polymer can then be soluble in hot xylene with the exception of small residues after removal of the Diluents by treatment with methanol which consisted of unreacted titanium metal, and hydrochloric acid conveniently from inorganic substances. From the solution in xylene, one fell out on cooling free mixtures. 65 gelatinous mass, which after washing out the

According to the process according to the invention, xylene and methanol have approximately the same properties Lent ethylene polymers are suitable as lubricants like the product obtained according to Example 1. at additive, plasticizer for polyethylene and - during the distillation of the benzene solution, 60 g high-

Boiling hydrocarbon oils and some hexaethylbenzene with a melting point of 128 ° to 130 ° C. were obtained.

Example 3

4 g of zirconium tetrachloride, 16 g of titanium trichloride and 5 g of aluminum powder were mixed and heated for 4 hours at a pressure of 17 mm. The temperature was gradually increased from 200 ° to 320 ° C. After the aluminum chloride which had crystallized out in the colder part of the tube had been separated off, 17.4 g of catalyst mixture were removed and flushed into the autoclave with 200 ecm of methylcyclohexane. In the treatment with ethylene under pressure, the reaction started at 115 ⁰ C and was performed with gradual temperature increase to 200 ° C within 7 hours of the end. The autoclave then contained 255 g of an almost black, rubber-like elastic mass. The catalyst was destroyed by heating with 200 ecm of methanol and 10 ecm of concentrated ammonia solution under pressure to 200 ° C. and the polymer was obtained as a uniform, light gray, elastic lump. Yield g. The product could be ^{pressed at 150 °} C. to give a plate with good elastic properties and contained 7% ash constituents.

Claims (1)

Claim: Process for the production of polyethylene by polymerizing ethylene in anhydrous liquid suspending agents in the presence of catalysts made from compounds of metals the IV. subgroup of the periodic system, characterized in that as a catalyst a zirconium compound in which the zirconium has a value less than 4 and the by reducing zirconium tetrahalides using aluminum or titanium is, is used, optionally with the addition of activated titanium, low-value titanium compounds or Friedel-Crafts catalysts.