DE1214401B - Process for the polymerization of propylene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

& I8UÖTKEK

OF THE OEUTSCHEK

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Int. CL:

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C08f

German class: 39 c -25/01

1214401
B65263IVd / 39c
December 20, 1961
April 14, 1966

It is known that propylene with Ziegler catalysts, for example from alkyl compounds of aluminum and / or beryllium and compounds, in particular halogen compounds of the metals of the IV. to VIII. subgroup of the periodic System, can polymerize, This is generally done in inert solvents, especially in Saturated hydrocarbons, such as pentane, heptanes or low-boiling gasoline fractions, polymerized in suspensions or solutions, and each is obtained Grams of catalyst about 200 to 300 g of propylene polymer, which has an isotactic content of at most 90%. The isotactic portion of the Polymer is generally considered to be part of the total solid polymer that is insoluble in boiling heptane, the quantitative precipitation z. B. obtained with methanol is determined.

It is also known that ethylene and propylene using Ziegler catalysts in Can polymerize in the absence of solvents. This is obtained from propylene per gram of catalyst 80 to 100 g of polypropylene with an isotactic content of at most 90%.

In addition, a process is known in which the polymerization of propylene in suspension using Ziegler catalysts, which by adding polyvalent amines, polyvalent Ethers and / or modified by amino ethers, polymerized. In this known method about 8 to 15 g of propylene polymers are obtained per gram of catalyst, the one isotactic Share up to about 90%.

There is also a polymerization process for propylene described in the Ziegler catalysts, which by adding monoethers, monoamines or thioethers modified can be used. About 60 to 80 g are obtained per gram of catalyst Polypropylene with an isotactic content of up to about 94% when working in suspension. Even in the polymerization of propylene in the absence of solvents using Ziegler catalysts, by adding monoamines such as pyridine, triethylamine, N, N-dimethylaniline and Diethylamine, modified, propylene polymers are obtained with an isotactic content below 85% with catalyst yields of at most 300 g of polymer per gram of catalyst.

In the known processes, the polymerization is carried out at pressures between normal pressure and about 40 atm. and carried out at temperatures between normal temperature and 150 ° C.

It has now surprisingly been found that processes for the polymerization of propylene

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Lufwigshafen / Rhein

Named as inventor:

Dr. Joachim Stedefeder, Lampertheim;

Dr. Hans Leitenschlagef,

New York, N.Y. (V. St. A.)

particularly high yields of propylene polymers with an isotactic content of over 90% is obtained when propylene or a mixture of a predominant amount of propylene and others is used Monoolefins using catalysts made from alkyl compounds of aluminum and / or Beryllium, halides of titanium and polyvalent ethers, polyvalent amines, amino ethers and / or Aminoketones in the presence of fine-grain propylene polymers and in the absence of solvents or polymerized in the presence of at most such amounts of inert solvents that the propylene polymers as a fine-grained, dry, mass can be obtained. In the new process, the reaction mixture is moved mechanically. During the polymerization the pressures are between normal pressure and 40 atm., preferably between 3 and 20 atm., and the temperatures between room temperature and 150 ° C, preferably between 60 and 120 ° C.

Alkyl compounds of aluminum and beryllium suitable as catalyst components have im generally identical or different alkyl radicals having 1 to 4 or even more carbon atoms, and the alkyl radicals can be straight-chain or branched. Examples of suitable alkyl compounds of aluminum and berylliums are diethyl aluminum chloride, ethyl aluminum sesquichloride, aluminum triethyl, Aluminum triisobutyl and beryllium diethyL Particularly suitable alkyl compounds are triethylaluminum, Diethyl aluminum chloride, ethyl aluminum sesquichloride and beryllium diethyl.

Chlorides are preferred as the halides of titanium. Examples of titanium halides are titanium tetrachloride, Titanium trichloride, titanium tetrabromide, titanium tetraiodide. Titanium tetrachloride is preferably used, Titanium tetrabromide, especially titanium trichloride.

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Polyvalent partial propylene polymers are suitable as polyvalent amines. Included

straight-chain, branched or cyclic aliphatic, the catalyst component can be separated or

Amines, such as N-methyl-dipropylenetriamine, Ν, Ν'-tetra- are applied together. It is also in some

methylethylenediamine, piperazine, hexamethylene tetra cases are advantageous, the catalyst first in

min and N- (3-aminopropyl) pyrrolidine. Also make more suspension and then if necessary

valuable aromatic amines such as benzidine, Ν, Ν'-tetra activated by heat treatment. Catalytic converter

methylbenzidine, and also polyvalent heterocyclic ones, if necessary after separating off the solvent

Amines, such as 3-amine pyrimidine and pyrazine, can be mixed with the propylene polymer; As a solution

be used. Straight-chain agents are preferred, those are suitable which are among the polymer

and branched aliphatic amines and hetero- ίο sationsbedingungen not with the catalysts or

cyclic amines. - "- _ Propylene react, like aliphatic in particular

Suitable polyvalent aliphatic ethers are hydrocarbons with boiling points between 35 and Diethylene glycol diethyl ether, triethylene glycol diethyl- 150 ° C, for example pentane, heptanes and low ethers, Propylene glycol diethyl ether and butylene glycol boiling gasoline fractions. However, their amount is like that. Diethyl ether or asymmetrical glycol ethers, 15 to be measured that they are from the finely divided propylene such as Diethylene glycol ethyl butyl ether. Multi-component polymer can also be absorptively absorbed, so that term aromatic, polyvalent araliphatic and the mixture as a fine-grained, "dry" mass pre-polyvalent heterocyclic ethers, such as 1,2-dimethoxy- lies. Mixing catalyst and finely divided benzene and 1,4-diethoxybenzene are possible. Propylene polymer can be separated from the polymer straight-chain aliphatic ether are suitable for the sation vessel and the mixture of this with two to eight ether groups in the molecule, which are then fed through continuously or discontinuously 2 to 6 carbon atoms are separated from each other. You can use the catalyst or the catalyst Diethylene glycol diethyl ether, triethylene glycol di-satorkomponenten but also the finely divided pro-ethyl ether and dibutylene glycol diethyl ether. pylene polymers in the polymerization vessel during

Possible amino ethers are those which add themselves to the polymerization of propylene. These

of straight-chain, branched and cyclic alipha mode of operation is particularly important in the case of continuous

tables as well as aromatic, also preferred by aralipha polymerize, as in the process

table hydrocarbons with 2 to 8 carbon - finely divided propylene polymers are formed, which themselves

derive atoms. Also heterocyclic amino ethers, are suitable as carriers and grain diameters in the above

such as oxazole and 4-ethoxypyridine are suitable. 30 have mentioned area.

Examples of aliphatic amino ethers are 3-methoxy. During the polymerization, the reaction propylamine and ethylene glycol ethyl-γ-aminopropyl mixture is moved mechanically. This can be done through intenäther. Suitable aromatic and araliphatic active stirring are carried out. The heat of polymerization amino ethers are / 5-phenoxyethylaniline and 4-ethoxy can, for example, through the wall of the reaction ethylaniline. The amino ethers are straight-chain aliphatic vessels and / or tables amino ethers with one to four amino and one by introducing cold propylene. Polymerization is particularly advantageous with up to four ether groups in the molecule. carried out in a fluidized bed.
Examples are 3-methoxypropylamine, 3-butoxy- The process is particularly suitable for homopropylamine and diethylene glycol ethyl-γ-aminopropyl polymerization of propylene. It is also suitable for interpolymerization with monoolefins, such as

In addition, amino ketones are suitable, which are particularly ethylene and also butene-1 and 4-methyl

l-Amino-pentanone- (4), l-diethylamino-pentanone- (4) pentene-1, with predominant amounts, d. H. in space-

andl-cyclohexylamino-hexanone- (5) of straight-chain, mean more than 70%, preferably 80 and more

branched or cyclic aliphatic carbon percent, propylene, based on the total amount of

Discharge hydrogen. Also aromatic and aralipha- 45 polymerizing olefins.

tables and heterocyclic aminoketones, such as p-Ami- In the process, it is often advantageous to use in Gegenno-benzophenone, l-dibenzylamino-pentanone- (4) and wa from molecular hydrogen or zinc alkylene, 3-acetylpyridine are possible. Straight-chain or z. B. zinc diethyl or zinc dipropyl, which act as a regulator only slightly branched aminoketones are especially used to polymerize. Hydrogen is a suitable example. In general, the molar ratio is 50 wise in amounts of 0.01 to 10 percent by volume, of alkyl compounds of aluminum or beryllium based on the volume of propylene, zinc alkyls in to the halide of titanium between 0.1: 1 and 10: 1, amounts Ύοη 5 to 50 percent by weight, based on preferably between 1: 1 and 5: 1. The molar the weight of the modified catalyst, as a regulator Ratio of alkyl compound of aluminum is suitable. Other suitable regulators are alkyl or and / or beryllium to polyvalent ethers, polyvalent aryl halides.

valuable amines and / or amino ethers and / or the process gives propylenepoly-

Aminoketones are generally between 10: 1 merisate, their isotactic, in boiling heptane

and 1: 1, preferably between 8: 1 and 4: 1. The insoluble fraction is over 90%, mostly over 92%.

Polymerization is carried out in the presence of fine-grained pro The catalyst yields are in general

pylene polymers, which generally have a grain size of between 400 and 600 g of polymer per gram

diameter between 0.5 and 3 mm, preferably of catalyst or more. An advantage of the procedure

about 1 mm. The fine-grained one can be seen in the fact that no after polymerization

Polymers act as supports for the catalysts or only extremely little solvent is removed.

and are expediently in amounts between 0.1 and must be separated. Another advantage is

4 kg, preferably between 0.2 and 1 kg per gram 65 that the polymer directly during the polymerization as

Total catalyst (calculated without solvent) easy-to-handle granules is obtained. A

used. The catalysts are, where appropriate, a particular advantage of the process is that one with

suspended in inert solvents, to the fine-an isotactic proportion in the polymer of over

90% catalyst yields achieved, which are at least about twice as large as when using propylene polymerized in suspension under otherwise identical conditions.

From the polymers, the catalyst residues can, if necessary, in a conventional manner, for. B. by Washing with aqueous-alcoholic hydrochloric acid. The process products are suitable for the production of shaped structures such as threads, fibers, films, foils, coatings and moldings.

The parts mentioned in the following examples are parts by weight.

example 1

In an autoclave, a mixture of 1.9 parts of titanium trichloride, 4 parts of triethylaluminum, 0.69 parts of diethylene glycol diethyl ether and 250 parts of light gasoline with a boiling point of 70 to 110 ° C. is added to 1500 parts of fine-grain polypropylene with an average particle diameter of 2 mm Autoclave and polymerize first 5 hours with stirring at 70 ° C and a pressure of 6 atm. and then another 5 hours at 70 ° C and a pressure of 9 atm. 3000 parts of polypropylene are additionally obtained, which has a heptane-insoluble (isotactic) proportion of 94% and the intrinsic viscosity [η] = 8.1 (100 ccm / g). The catalyst yield is accordingly 450 parts of polypropylene per 1 part of catalyst.

If, instead of 0.69 part of diethylene glycol diethyl ether, 0.48 part of pyridine is used to modify the catalyst, an additional 2700 parts of polypropylene, which has an isotactic content of only 85%, are obtained under otherwise identical conditions during the polymerization. The yield in this case is 420 parts of polypropylene per 1 part of catalyst and the intrinsic viscosity [η] = 7.2 (100 ccm / g).

Example 2

Propylene is polymerized as described in Example 1, using a modified catalyst which contains 0.77 part of N- (3-aminopropyl) pyrrolidine instead of 0.69 part of diethylene glycol diethyl ether. In addition to the initially charged polypropylene, 2500 parts of polypropylene are obtained, which has an isotactic content of 91.5% and the intrinsic viscosity [η] = 7.1 (100 ccm / g). The yield in this case is 400 parts of polypropylene per 1 part of catalyst.

Example 3

Propylene is polymerized, as indicated in Example 1, using a modified catalyst, for the preparation of which 1.18 parts of ethylene glycol ethyl-γ-aminopropyl ether were used instead of 0.69 parts of diethylene glycol diethyl ether. An additional 3200 parts of polypropylene are obtained, which has an isotactic content of 93% and the intrinsic viscosity [η] = 8.3 (100 ccm / g). The yield in this case is 450 parts of polypropylene per part of catalyst.

Example 4

Propylene is polymerized, as indicated in Example 1, using a modified catalyst which contains 0.71 part of 3-methoxypropylamine instead of 0.69 parts of diethylene glycol diethyl ether. An additional 3200 parts of propylene are obtained, which has an isotactic content of 91.7% and an intrinsic viscosity [η] - 8 (100 ccm / g). The yield is 480 parts of polymer per 1 part of catalyst.

Example 5

Propylene is, as indicated in Example 1, polymerized using a modified catalyst which contains 2.1 parts of 1-diethylamino-pentanone- (4) instead of 0.69 parts of diethylene glycol diethyl ether. An additional 3200 parts of polypropylene are obtained, which has an isotactic content of 90.1% and an intrinsic viscosity [η] - 7.8 (100 ccm / g). The yield is 400 parts of polypropylene per 1 part of catalyst.

Claims (1)

Claim: Process for the polymerization of propylene or a mixture of a predominant amount Propylene and other monoolefins to form high molecular weight polymers with an isotactic one Share of over 90% using catalysts made from alkyl compounds of aluminum and / or beryllium, halides of titanium and ethers and / or amines in the presence fine-grained propylene polymers and in the absence of solvents or in the presence at most such amounts of inert solvents that the propylene polymers as fine-grained, dry mass can be obtained at pressures between normal pressure and 40 atm. and Temperatures between room temperature and 150 ° C with mechanical agitation of the reaction mixture, optionally in the presence of hydrogen, zinc alkylene, alkyl or aryl halides as a controller, characterized that as ethers and / or amines in a known manner polyvalent ethers, polyvalent Amines, amino ethers and / or amino ketones can be used. Considered publications:
French Patent No. 1,253,455;
interpreted documents of the Belgian patent
407 609 558/437 4.66 © Bundesdruckerei Berlin