DE1203473B - Process for the polymerization of ethylene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C08f

German class: 39 c -25/01

Number:
File number:
Registration date:
Display day:

1203 473
P18251IVd / 39c
March 29, 1957
October 21, 1965

The polymerization of olefins is known and is generally carried out in the presence of a catalyst executed. In recent years there has been a great deal of interest in the development of catalysts which in the polymerization of olefins, especially ethylene, can be used to solid polymers to arrive. The solid polymers so produced can be made into molded articles such as Lines, containers for liquids, protective coatings and insulation are processed. While Compounds of silicon dioxide and aluminum oxide are often used as carriers for other compounds in Catalyst systems and used as catalysts in the polymerization of olefins such as propylene to form liquid polymers, it was generally believed that silica- Aluminum oxide is not used on its own as a catalyst for the production of solid polymers of ethylene could be. It has now been found that solid polymers are formed from ethylene when Ethylene in contact with a silica-alumina catalyst under polymerization conditions is brought.

The inventive method for the polymerization of olefins in the presence of inert liquid hydrocarbons by means of catalysts made of silicon dioxide and aluminum oxide, which are produced by heating in Air has been activated at elevated temperatures and pressures is that ethylene is at Temperatures in the range from 93 to 177 ° C and pressures from 14 to 49 atm is polymerized.

The catalyst used in the process of the invention consists of silica and Aluminum oxide and can be a gel produced by coprecipitation or impregnated. The content of silicon dioxide and aluminum oxide in such a catalyst can be within wide limits fluctuate, e.g. B. from 0.5 to 99.5% alumina with the remainder being silica. In the case of one The alumina content is preferably the same as the catalyst obtained by coprecipitation between 3 and 50 percent by weight, while in the case of an impregnated catalyst the aluminum oxide content is preferably from 0.5 to 10 percent by weight, the remainder in each case being silica is. A particularly effective material is an industrially available cracking catalyst in the mold of a co-precipitated gel of silica and alumina which is about 90 percent by weight Contains silicon dioxide and approximately 10 percent by weight aluminum oxide. Another technically accessible material that can be used Process for the polymerization of ethylene

Applicant:

Phillips Petroleum Company, Bartlesville, OkIa.

(V. St. A.)

Representative:

Dr. F. Zumstein

and Dipl.-Chem. Dr. rer. nat. E. Assmann,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Named as inventor:

Robert Louis Banks, Bartlesville, OkIa.

(V. St. A.)

Claimed priority:

V. St. v. America March 29, 1956 (574 609)

can, is commercially available as "Phillips silicon oxide-aluminum oxide catalyst" known, which by moist impregnation of a freshly prepared silica gel with a solution of an aluminum salt, washing the activated gel and drying it will be produced.

In the method according to the invention, a solvent is used as a reaction medium and / or as Medium used to recover the polymer. Suitable solvents are hydrocarbons, which are liquid and chemically inert under the process conditions. Solvents which are advantageously used are paraffins, especially those with 3 to 12 carbon atoms in the molecule, z. B. 2,2,4-trimethylpentane (isooctane), n-hexane, η-decane, isopentane and the like but also naphthenic hydrocarbons, such as cyclohexane and methylcyclohexane, can be used.

The contacting of the reactants with the catalyst can be carried out by numerous known methods Methods are effected, e.g. B. in a fixed or moving catalyst bed or in systems that one use suspended catalyst.

If a moving or fixed catalyst bed is used, the ethylene concentration is in the solvent in the reaction zone generally 0.5 to 20 percent by weight of the total input, preferably 1 to 10 percent by weight. The solvent also serves as a coolant for the reaction zone and as a solvent for the

509 718/502

3 4

Ethylene and the polymer produced, after 4 hours the ethylene supply was stopped

Removal of the product from the reaction zone and all ethylene from the reactor by continuous

is made easier. When a moving catalyst bed lent circulating isooctane rinsed out. The reactor

is used, it is desirable when the temperature has been emptied, the catalyst has been emptied from the reactor

tures in which the polymer is removed in a 5 and what is deposited on the catalyst

larger proportion is not soluble. In this case it definitely serves. The recovered polymer was in one

the solvent only heated as a solvent for the vacuum oven to remove isooctane.

Ethylene. If the polymerization takes place in a moving The proportion of the precipitated on the catalyst

Catalyst bed is carried out, e.g. B. in a gene and recovered polymer was the following:

mechanically stirred reaction space or in an io

Fluidized bed reactor, the ratio of solid polymer can be 1.4 g

Ethylene to solvent are higher than in reac- _{precipitate on the kata} .

gates with a fixed bed. This follows from the _fact j toJ. ⁶ _{3 g} (high molecular weight

thing that with stirred and fluidized bed reactors' ^e p _o i _vmeres ·)

a better heat transfer can be produced 15 y)

It was determined by orsat analysis that 18%

remove heat from the reaction zone. or 9.4 g of ethylene had been converted.

The process according to the invention is carried out at a 55% of the converted ethylene as a never-temperature between 93 and 177 ° C and at a derschlag on the catalyst and as a solid poly pressure that is sufficient to produce a liquid ao meres.
Maintain phase in the reaction zone. The- Example 2
this pressure is between 14 and 49 at.

To better explain the invention, the ethylene was said to be using the same catalyst that-

The following examples are used. same gas feed and same solvent

25 according to the procedure as described in example 1

Example 1 polymerized _ben j _stj. Approximately 59.8 grams of catalyst

It was ethylene in the presence of a silicon were used and the polymerization at a

Dioxyd-aluminum catalyst using temperature between 116 and 121 ° C at a

of a fixed bed reactor. Pressure of 31.5 at and a throughput speed

The reactor used was constructed from a 76 cm length for the liquid of 6 parts by volume of liquid and 3.54 cm wide seamless tube, per part by volume of the catalyst per hour surrounded by a soft 38 mm tube which was guided. The duration of the experiment is 4 hours, the heat transfer fluid, namely water, contained the proportions of deposited on the catalyst. An electric heater surrounded the jacket, and the polymers obtained were as follows:
and the top of the mantle was covered with a condensate 35

gate connected. Carbon dioxide was used to control ^solid polymer 2.7 g

of the pressure of the boiling water in the mantle, precipitation on the cata-

led, the reaction temperature controlled lysator 4.0 g (high molecular weight

became. A thermocouple sleeve was provided, polymer)

which extends from the bottom to the center of the reactor 40

extended. The solid polymer was treated with isooctane for loading

Thermocouple sleeve for receiving the catalyst mood extracted from the soluble fraction. It was

tied together. found 74% of the polymer in isooctane

The tableted catalyst was insoluble in an amount 29 ° C. It was also made by Orsat-

of 58.3 g, the 90 percent by weight silicon dioxide analysis determines that 19% or 9.9 g of ethylene

and containing 10 weight percent alumina. 68% of the converted ethylene

applied after having previously been at for 5 hours as a catalyst precipitate in the form of a

510 ° C had been activated with dry air. solid polymers obtained. The insoluble in isooctane

The gaseous feed contained approximately 75% boron polymers and was analyzed and found to be technical ethylene and 25% pure ethane. The 50 found that it has the following properties:
Circulating solvent was pure isooctane, which ThHT
has been pretreated to remove oxygen ^ae
was. - molecular weight (calculated

The gaseous filling was with the reverse viscosity) 10 600

Isooctane used and then mixed into the viscosity of 0.439

Inserted the top of the reactor. These materials density 0.973

were in the reactor in the following proportions _to-s, nunkt 119 * +2 ⁰ C

Ethylene 13.0g / StA ^ Example 3

Ethane 5.4 g / h Ethylene was in the presence of a silica

Isooctane 41.7 g / h Alumina catalyst using a

1-1 reactor, which is equipped with a jacket and a

The polymerization was carried out at a temperature by means of a motor-driven stirrer, poly-intermediate 110 and 121 ° C merized at a pressure of 65.

31.5 at and a throughput rate of 3.04 g (0.8 to

Liquid of 6 parts by volume of liquid per volume - 0.5 mm clear mesh size) and consisted of 90 parts of the catalyst carried out per hour. weight percent silicon dioxide and 10 weight percent

Claims (1)

5 6 cent aluminum oxide, which must be kept dry at 510 ° C with 31.15 atm, filled into the reactor. The air had been activated for 8 hours. The reactor temperature was changed by manual change. Catalyst was introduced into the reactor along with 417 g of hydrogenated carbonic acid pressure on the boiling water in cyclohexane. The catalyst jacket was kept at approximately 132 ° C, was in the solvent by means of a motor- 5 The duration of the experiment was 4 hours. Maintained in suspension at the end of the driven stirrer. Tech- this period the reactor was allowed to cool, after which ethylene was fed into the reactor in an amount after the polymer was removed from the reactor, of 64 g / h. and thereafter at a rate. The polymer was then dried and introduced as sufficient to treat the pressure in the reactor to 32.2 at Example 3 to remove the catalyst. The reactor temperature became ionized. About 22.2 grams of solid polymer was recovered by manually changing the carbon dioxide. This ethylene polymer was analyzed, pressure on the boiling water in the reactor and found to be kept in the following jacket at approximately 132 ° C. The duration possessed the properties given in Table III.
Trial was 4 hours. At the end of this period the reactor was allowed to cool, after which the reactor 15 labeile 111 opened and the polymer removed. The poly molecular weight (calculated mere was dried in a vacuum oven until it came out of viscosity) 56,300 constant weight. The dried polymer viscosity 2.34 was then added to cyclohexane, which was reduced to a density of 0 95 was heated to about 163 ° G. The resulting solution 20 1 "'i, 11 o'4- 00 r> of the polymer in cyclohexane was then filtered bcümeizpunkt lly ± l c to remove the suspended catalyst. That impact resistance Cyclohexane was then evaporated and the polymer (falling ball method) > 183 cm in a vacuum furnace up to constant weight flexibility good dries. Approximately 0.82 g of solid polymer was added the won. This ethylene polymer was analyzed in each of the above examples and it was found that the catalyst in Table II was a coprecipitation of the possessed specified properties. Components manufactured catalyst. The manufactured according to the method of the invention Table II 30 th polymers are useful where rigid synthetic molecular weight (to be used of ^materials is calculated. You can for Imprägnieder viscosity) pi 55 000 ¹¹¹¹¹ S ^of P ^{a he un} serve d tissues, and they can viscosity 2 30 ^to g ^{e shaped} articles of any desired shape 'are melted, e.g. B. to bottles. Furthermore, ,,. . ,. 35 they can be shaped into tubes by extrusion. Example 4 Ethylene was in the presence of a silica claim:
Polymerized alumina catalyst using the same type of reactor as in Example 3. Process for the polymerization of olefins in The amount of catalyst was 59.5 g (0.8 to 40 presence of inert liquid hydrocarbons, 0.2 mm mesh size). It consisted of 90% by weight catalysts made of silicon dioxide and weight percent silicon dioxide and 10 weight per cent aluminum oxide, which had been activated by heating in air, which had been activated with active aluminum oxide at 510 ° C, at elevated temperatures in air for 5 hours. The and pressures, characterized in that the catalyst was introduced ^{into the reactor together with 277 g of hydrogenated 45 da} ß ethylene at temperatures in the range of cyclohexane. The catalyst 93 to 177 ° C and pressures of 14 to 19 at polytor was in the solvent by means of a motor-merized. driven stirrer kept in suspension. Tech Ethylene was initially considered with a maximum number of publications: Amount of 67 g / h and then at a speed 50 German Patent Specifications No. 858 394, 879 099; enough to control the reactor pressure in U.S. Patents Nos. 2,710,854, 2,780,617. 509 718/502 10.65 © Bundesdruckerei Berlin