DE1069877B - Process for the polymerization and copolymerization of terminally olefinically unsaturated hydrocarbons and of polyolefins with conjugated double bonds - Google Patents

Description

.y

FEDERAL REPUBLIC OF GERMANY

KL.

INTERNAT. KL. C 08 f

C08F 10, -00

EXPLAINING PUBLICATION 1069 877

D 26218 IVb / 39 c

REGISTRATION DATE: AUGUST 16, 1957

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: NOVEMB 26, 1959

The polymerization of terminally olefinically unsaturated hydrocarbons and of polyolefins with conjugated double bonds under mild conditions is due to the work of Ziegler and known to others. The essential feature of such polymerizations is that they use a catalyst system by mixing an organometallic compound of a metal of the first three groups of the periodic system with a compound of a metal of subgroups (a) of groups IV up to VIII of the periodic system (compare e.g. the Belgian patents 533 362, 534 792 and 538 782).

Many different catalyst systems for polymerizations of olefins are described. the best results have been obtained with systems containing triethyl aluminum as one of the components. Aluminum triethyl is made by reacting aluminum with olefins and hydrogen in the presence of an aluminum alkyl prepared under high pressure and at high temperature. Aluminum triethyl etherate On the other hand, it can be easily selected from anhydrous aluminum chloride and a suitable one Grignard reagent, e.g. B. ethylmagnesium bromide. The ether is solid with the aluminum triethyl connected, and there is no method of producing free aluminum triethyl from it known to its etherate. However, aluminum triethyl etherate does not form effective catalyst systems type described above, and the yield of polymer according to the amount of aluminum used is not high enough for technical purposes. Furthermore the ether hinders this kind of polymerizations, and accordingly the polymerization is slowed down if the etherate is in the course of the Reaction decomposes and forms free ether.

The aim of the present invention is to provide a process for the polymerization of olefinically unsaturated hydrocarbons of the formula CH ₂ = CHR, where R is hydrogen, alkyl, cycloalkyl or aryl, and of polyolefins with conjugated double bonds, in which one component of the catalyst system consists of a Complex, which can easily be prepared from the aluminum triethyl etherate and contains no ether residue. The process gives - based on the amount of aluminum present - greater yields of polymer than aluminum triethyl etherate under similar polymerization conditions. The catalyst system used is a mixture of a compound of a metal from groups IV to Villa of the Periodic Table and a solid complex compound obtained by reacting an alkali metal with aluminum triethyl etherate.

Polymerization process

and interpolymerization

of terminally olefinically unsaturated

Hydrocarbons

and of polyolefins

with conjugated double bonds

Applicant:

The Distillers Company Limited,
Edinburgh (Great Britain)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:
Great Britain 17 August 1956

Irene Marianne Watt, née Cohen,
Epsom, Surrey (UK),
has been named as the inventor

The new essential component of the catalyst system, for the manufacture of which no protection is sought is the solid reaction complex of alkali metals with aluminum triethyl ether. These Reaction is easy to take place and is carried out by adding the alkali metal, preferably in a form with a large surface area, with the aluminum triethyl etherate in an inert diluent is heated.

A suitable method for carrying out the reaction is that the alkali metal and the aluminum triethyl etherate in an inert diluent, e.g. B. a hydrocarbon, such as petroleum ether, which has a boiling point such that the reaction can be carried out under reflux conditions is heated. Suitable reaction rates are obtained by subjecting the reaction mixture is maintained at a temperature between 50 and 150 ⁰ C.

Any alkali metal can be used, but the use of sodium is preferred.

The complex formed by the reaction of sodium and aluminum triethyl etherate is

909 650/564

3 4

temperature, ζ. B. 20 ° C, a crystalline solid body z. B. nitrogen or argon, for purging the

and has to be used as a poly polymerization vessel compared to aluminum triethyl. The cata-

merization catalyst has the advantage that it is in dryer systems and / or their components

is not pyrophoric in air. The reaction complexes by reaction with oxygen, carbon dioxide or

of the other alkali metals have similar water properties. It therefore finds only a small one

stocks. or no polymerization at all, if one of the

The formation of the solid complex from alkali substances is present in excess. Small amounts

metals and aluminum triethyl etherate will be replaced by oxygen, carbon dioxide or water

accompanied by a deposition of aluminum, which can easily be reacted with part of the catalyst

removed by decanting the molten product io systems or its components, and the

can be removed. Even excess alkali, undestroyed catalyst remaining after this reaction

metal can be removed this way. Water initiates the polymerization in the usual way.

At the end of the reaction, ether is released, and that from the reaction is most conveniently the polymerization

tion mixture must be removed. carried out when the reaction components in

That for the preparation of the solid complex are well dispersed in an inert liquid medium,

applied ratio of sodium to aluminum- especially when the monomer to be polymerized

Triethyl etherate is not essential because excess! - is normally a gas. Appropriately this is

the non-volatile, solid, inert liquid medium can become a solvent for little

Product due to distillation and excess alkalinity is one of the factors that lead to the formation of the catalyst system

metal can be removed by decanting. Around the 20 reacting compounds and for the

Maximum yield of product with a minimum loss of hydrocarbon to be polymerized. Examples

of starting material is the most suitable liquid media are aliphatic, cyclo-

preferred molar ratio of alkali metal to aluminum aliphatic and hydrogenated aromatic hydrocarbons

Minium triethyl etherate about 3: 4. fabrics, e.g. B. pentane, hexane, cyclohexane, tetrahydro

The process according to the invention is carried out using mil-naphthalene, decahydronaphthalene and mixtures

the temperature and pressure conditions in one of them. The amount of solvent used can

Carried out in a manner that varies considerably in the procedures below and is intended to be so sized

Be using the known catalyst systems that the final recovery of the polymer

two components in the above-mentioned literature is facilitated,

places is indicated. 30 The catalyst used according to the invention

The systems used in the process according to the invention can be sufficiently effective to remove the poly compounds of the metals of groups IVa to merization at normal room temperature or Villa of the Periodic Table (cf. H. Remy, lower, e.g. 10 ° C, to initiate the Polymerisa textbook der inorganic Chemie, 7th edition, tion speed is usually by Er-Vol. 1, 1954, p. 10) are the same as the previously used increase in the temperature of the reaction mixture and auctioned as described in the art. The use of temperatures above bonds for the polymerization of α-olefins. however, about 150 ° C is usually not wün-preferred Metals are titanium, zirconium and vanas worth seeing. It should be noted that above this dium, of which the former is the easiest temperature there is a danger that the action of the is available and gives the best results. It reduces or even destroys the 40 catalyst system are many different compounds these metals will be.

proposed as components for catalyst systems The process by which the invention

have been gen, and of these in the invention-produced polymer from the reaction mixture

produces similar results according to the procedure. Acquired and processed into its final form

games are acetates, acetylacetonates, oxyhalogen salts, 45 will is insignificant. However, it is beneficial

z. B. oxychloride, halogen complexes, e.g. the metal during work-up a washing with a

fluoride complexes, and freshly precipitated oxides or mineral acids to remove metallic impurities

Hydroxides. The most suitable connections are to make the connections. The procedure can be

Halides of the metals, and the preferred compounds, or carried out continuously and by

fertilizers contain titanium tetrachloride, titanium trichloride and high-quality polymers

Titanium dichloride. will.

That used to form the catalyst system is particularly suitable for the polymerization of

dete ratio of the alkali metal aluminum triethyl ethylene and propylene. Special examples for others

etherate complex to the metal compounds can be suitable monomers are n-butene-1, n-pentene-1 and

vary greatly. However, it will use 55 n-hexene-1. Copolymers of such compounds

a molar excess of the complex before- with each other or with other co-polymerized

admitted. As a molar proportion of the reaction complex, hydrocarbons can also be used

an amount of the complex is considered to be such that the process according to the invention is formed.

Contains 1 gram atom of aluminum. Typical polymerizable and copolymerizable

The preparation of the catalyst system using 60 bare polyolefins with conjugated double bonds mixing the alkali metal aluminum triethyl etherate are 1,3-butadiene, isoprene and piperylene.
Complex with the metal compound and the following example illustrates exclusive polymerization are preferably carried out in the process of the invention.
In the absence of molecular oxygen, carbon dioxide and water. Using the practical example

Most of the reactions are carried out in an inert atmosphere. Under a nitrogen atmosphere there are 17 spheres or in an atmosphere of the sodium wire to be polymerized by weight in petroleum ether (boiling range Renden hydrocarbon carried out, if this 100 to 120 ° C) pressed and 188 parts by weight of Aluein Gas is. Triethyl etherate was added before the various components were added. You heat them up uenten the reaction mixture can be an inert gas, 70 mixture under reflux for 2 hours and then leaves

Claims (3)

I 069 877 cool, whereby a lower layer separates, which solidifies. The upper liquid layer, which contains the ether originally present in the etherate, is poured off and the complex washed by decanting with petroleum ether. The complex is melted, decanted off and separated from the aluminum formed, after which it is then dried over animal charcoal under reduced pressure. A suspension of 3 parts by weight of the complex in 400 parts by volume of petroleum ether (boiling point 100 to 120 ° C) is placed in a stainless steel reaction vessel with a capacity of 1000 parts by volume and the mixture is poured at a pressure of 1.75 kg / cm2 and a temperature of 40 ° C saturated with propylene. 1 part by weight of titanium tetrachloride is added and the mixture is stirred for 5 hours, further propylene being added to maintain the pressure in the system. After this time, the reaction vessel is opened and its contents washed with methanol and a hydrochloric acid-methanol solution. 20 g of white polypropylene are obtained which contain 83% of crystalline product. This corresponds to a yield of 41 parts by weight of polypropylene per unit weight of aluminum in the catalyst system. The same catalyst system is similarly effective in polymerizing ethylene, butadiene and isoprene under substantially the same polymerization conditions. Similar effective catalyst systems are obtained by replacing the titanium tetrachloride used above with an equivalent amount of zirconium or vanadium tetrachloride. For comparison, two similar polymerization systems were used which differed only in that the reaction complex was replaced by aluminum triethyl etherate or aluminum triethyl. Both systems caused propylene to polymerize. The catalyst system obtained from the etherate gave 4.8 parts by weight of propylene per unit weight of aluminum in the catalyst system, and the system obtained from aluminum triethyl gave 45 parts by weight of polymer per unit weight of aluminum in the system. ίο patent claims: 1. A process for the polymerization and copolymerization of olefinically unsaturated hydrocarbons of the formula CH ₂ = CHR, where R is hydrogen, alkyl, cycloalkyl or aryl, and of polyolefins with conjugated double bonds in the presence of a catalyst combination of an organoaluminum compound and a compound of a metal of the groups IVa to Villa of the Periodic System, characterized in that a solid complex compound obtained by reaction of an alkali metal with aluminum triethyl etherate is used as the organoaluminum component. 2. The method according to claim 1, characterized in that one is used as an organoaluminum Component uses a solid complex made by heating an alkali metal with large Surface, especially of sodium, with aluminum triethyl etherate in an inert diluent at 50 to 150 ° C has been obtained. 3. The method according to claim 1 and 2, characterized characterized that as a compound of a metal from group IVa to Villa a titanium, zirconium or vanadium halide is used. 1 909 650/564 11.59