DE1240668B - Process for the production of solid, high molecular weight poly-alpha-olefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 c - 25/01

Number: 1240 668

File number: E 23545 IV d / 39 c

Filing date: September 20, 1962

Open date: May 18, 1967

It is known that in the catalytic polymerization of α-olefins it is possible to produce polymers which exhibit very different properties and very different physical behavior, which to a large extent depend on the catalyst system and the process conditions. Much work in this area has been devoted to the development of catalysts and catalytic processes which can form highly crystalline poly-α-olefins, ie those olefins with crystallinities of at least 70%> since it has been shown that these highly crystalline polymers over the amorphous poly -a-olefins have greatly improved properties. For example, having amorphous polypropylene which was formed after a few known processes as a solid body, a melting point of only 8O ⁰ C and a density of 0.85, while solid, highly crystalline polypropylene having a melting point of at least 165 and a density of 0.92. Similarly, 1-polybutene has a crystalline melting point of 120 ⁰ C and a density of 0.91, while amorphous polybutene-1 has a softening point of about 60 ° C and a density of 0.87. The same increase in density and melting point is observed with other x-olefins in solid, polymeric form, including the straight and branched chain monoolefins. Crystalline poly-3-methylbutene-1 has a melting point above 240 ⁰ C, crystalline poly-4-methylpentene-l has a melting point above 205 ⁰ C, crystalline poly-methyl hexene, 4-1 has a melting point of about 190 ⁰ C. Crystalline poly-5-methylhexene-1 has a melting point of the order of 13O ⁰ C, and crystalline poly-4,4-dimethylpentene-1 has a melting point of over 300 ⁰ C. It follows that polymerization processes and catalysts, which form highly crystalline polyolefins with crystallinities of at least 70% are of considerable importance in practice.

A number of processes have been described for making solid, highly crystalline poly- «- olefins, including e.g. B. the polymerization of ethylene and higher "olefins, such as propylene and butene-1, to form highly crystalline polymers in the presence of inert solvents at temperatures of 100 ^° C. or below and at relatively low pressures. Catalyst mixtures used in these so-called slurry processes comprise an aluminum compound, e.g. B. an alkyl aluminum, a dialkyl aluminum halide, an alkyl aluminum sesquihalide or lithium aluminum process for the production of solid,
high molecular weight poly-a-olefins

Applicant:

Eastman Kodak Company,

Rochester, N. Y. (V. St. A.)

Representative:

Dr.-Ing. W. Wolff and H. Bartels, patent attorneys, Munich 22, Thierschstr. 8th

Named as inventor:

Hugh John Hagemeyer Jr.,

Vernon Kee Park, Longview, Tex. (V. St. A.)

Claimed priority:

V. St. v. America October 18, 1961 (146 004)

genius of a transition metal. If the catalysts of this type are used at temperatures above 100 ^° C., however, the halide of the transition metal is reduced rapidly and an inactive catalyst is obtained. These known catalysts can therefore not be used for polymerization at elevated temperatures which allow the formation of the polymer near or above its melting point without the catalyst being contaminated or the system being inactivated. In addition, at elevated temperatures, the difficulties associated with many low temperature processes, with the formation of the polymer causing a precipitate on the catalyst, are avoided. This precipitate is sufficient to cause inactivation or, if the polymerization is carried out in a solvent medium, the polymerization mixture becomes too viscous to be properly stirred before the catalyst is exhausted. This makes the process less economical and requires that large amounts of residual catalyst be removed from the resulting polymer.

Another advantage of high temperatures over lower temperatures in the polymerization of «-Olefins is that the induction time for a catalyst decreases with increasing temperature. So give Natta and coworkers in »La Chimica

tetraalkyl, and a cocatalyst, e.g. B. a Halo e L'Industria «, 39, section 12 (No. 12), p. 1002

709 580/270

3 4

to 1012, 1957, particularly in Fig. 5, data on molecular polymers with very high crystallinity which illustrate that a temperature increase, ie with crystallinities of at least 70% from 32 to 70 ° C, shortens the time required to create. In this method of polymerization, a constant rate of polymerization at higher temperatures will reduce a catalytic 7 hours to approximately 2 hours. 5 mixture used, as opposed to near-ver At temperatures of at least 14O ⁰ C, preference towards mixtures of polymerizing "-Monoweise 150 ° C, this induction period is essential in the olefins to solid polymers is highly effective and avoided loan, of course provided that the catalyst does not possess an unusual degree of stereospecificity at these high temperatures, thereby inactivating the undesirable formation of low. It is also important, as Natta emphasizes in the same series of articles that molecular polymers, which are oily or greasy, are avoided and the formation of amorphous catalysts, such as aluminum alkyls and titanium trisolid polymers, is also considerably reduced,
chloride, lower crystals at higher temperatures. Catalylinities will result in the process according to the invention. used, which are easier and more even

Another important advantage of the solution polymer can be produced than the catalysts which can be produced by the merization process of -olefins at high temperature compared to the slurry process at high temperature, because the reaction product is low in the fact that in the process first mentioned from lithium hydride and aluminum trialkyl crystalline, the catalyst concentration is and by simply mixing lithium ions are generally so low that hydride and aluminum trialkyl can be obtained,
It is possible to simply filter the polymer solution. The process facilitates the preparation of the very useful, highly crystalline, solid poly-a-monotonous enough to obtain products with residual ash contents that are most practical anolefins, with hydrocarbon polymers having very high utility purposes to suffice. In contrast to melting points, high tensile properties, it is extremely difficult to separate a solid by good moldability, improved rigidity, and with chemical reaction and extraction, the improved film-forming properties are easily obtained by the low temperature slurry processes.

temperature must be applied. The invention also provides a method for avoiding the separation of a catalyst by producing solid, high molecular weight poly-a-ole filters and obtaining polymers by refining the solvent with a crystallinity of at least 70% at these high temperatures Polymerization of "monoolefins with mintur process the poisoning of the refluxing olefin at least 3 carbon atoms at a temperature and the solvent streams with polar solutions from 140 to 300 ° C, preferably 150 to 200 ⁰ C, and means, such as alcohols, which in these slurry atmospheric pressure to 2000 atmospheric pressure can be used at low temperature, 35 spheres in the presence of a catalyst mixture to wash the catalyst from the polymer. from a halide of titanium, vanadium, chromium, polar solvents, such as alcohols, are of course tungsten or molybdenum, in which the valency of the catalyst poisons, and therefore the olefin flowing back in the metal must be at least one valency level below the cycle and the maximum value of the solution , and a lithium demineralized stream in a slurry process at 40 holding component, which is highly purified by being characterized by a low temperature to remove these polar poisons in the presence of a catalyst. In the case of a high-mix polymerized, the lithium-containing temperature-dissolving process, however, need the oil component from the solid reaction product from fin and the solvent streams only filtered, concentrated lithium hydride with an aluminum trialkyl, whose trated and directly to the synthesis stage again in the 45 alkyl groups, preferably 1 To be returned to 12 carbon cycle without containing circumferential atoms, in a molar ratio of rich cleansing treatments that consists of the low-1: 1 to 10: 1.
temperature slurry processes are so necessary. The method according to the invention is extremely suitable

With a few notable exceptions that are effective in polymerizing “monoolefins”

US Pat. No. 2,908,670 describes 50 at least 3 carbon atoms, in particular the

(Lithium as a catalyst component), is the stand of straight and branched-chain aliphatic «mono-

technology is not sufficiently advanced to solidify olefins with 3 to 10 carbon atoms,

catalytic production of solid, highly crystalline, high molecular weight, highly crystalline polymers with

To allow poly-α-olefins at elevated temperature. excellent yield. The higher a-mono-

From the above discussion it appears that of the 55 olefins required for use in the implementation

Prior art suitable by such a catalytic of the invention include e.g. B. propylene,

Procedure is greatly enriched. In the same way butene-1, pentene-1, hexene-1, heptene-1, octene-1,

carries a catalytic process that catalyzes decene-1, dodecene-1, 3-methyl-1-butene, 4-methyl

sator mixture uses, which at elevated temperatures 1-butene, 4-methyl-1-benzene, 4-methyl-1-hexene, 5-Me-

tures for the formation of solid, high molecular weight poly- 60thyl-1-hexene, 4,4-dimethyl-1-pentene.

α-olefins with crystallinities of at least 70% As already stated, one component is the

is effective to enrich the state of the tech catalyst mixture of the solid, crystalline complex,

nik at. As a result of the insolubility of lithium, which occurs through the reaction of lithium hydride with tri

component, however, it is difficult to create catalysts alkylaluminum. The complex will

of uniform consistency. 65 easily formed by simply using the lithium hydride

The object of the invention is therefore to provide a new trialkylaluminum using suitable reaction processes is brought into contact for the polymerization of -monoolefinen conditions. Other alkali limits at least 3 carbon atoms to solid, high metal hydrides, z. B. hydrides of sodium or

5 6

Potassium, in the same way as lithium hydride dichlorides, can form one of the abovementioned complex compounds used with the aluminum trialkyls, particularly titanium chlorides. However, these complex compounds are not. The use of the complex compound which is effective catalyst components for forming by reaction of lithium hydride with a tri-highly crystalline polymer of higher mono-alkylaluminum constitutes a significant olefin at high temperatures. In the formation of progress in the catalytic polymerization of the active catalyst component, which is used in the α-monoolefins with at least 3 carbon atoms according to the invention, solid, high molecular weight, highly crystalline poly-lithium hydride and trialkylaluminum in one form. So lithium hydride itself cannot with a molar ratio in the range from 1: 1 to 10: 1 io the transition metal halides to form a reacted, preferably in the range from 1.5: 1 to active catalyst mixture for the polymerization 3: 1, with the formation of the solid complex, which in higher « -Olefins are used. Aluminiumtriinerten liquid organic media such as cyclo alkyls inactivate transition metal halides by hexane, decane, isooctane, and odorless petroleum over-reduction at temperatures above 100 ⁰ C. In the recovered solvents is insoluble. Inert, 15 in contrast, the solid, crystalline organic reaction forms liquid media that can be used to form the product of lithium hydride with trialkylaluminum complex, include all as described herein, when used with aliphatic alkanes or cycloalkanes such as pentane, lower valent transition metal halides of titanium, hexane, heptane, isooctane or cyclohexane or the chromium, vanadium, molybdenum or tungsten a high molecular weight liquid paraffins or mixtures 20 extremely effective catalyst mixture for poly of paraffins, which are at the reaction temperature merization of the said -olefins to solid, highly liquid. In addition, aromatic carbon-molecular, highly crystalline polymers. In addition, hydrogens such as benzene, toluene and xylene, with good ones, are the active catalyst complexes used in the results. The complex processes of the invention are used, suitably at temperatures in the range of 25 to higher "olefins, in which polymers and in about 25 to 100 ⁰ C, preferably in the range of from about the conditions used for carrying out the process 25 to about 100 ° C, formed. The reaction time depends on the inert organic, liquid carrier substances, usually on the temperature used, borrowed. They can therefore be removed by filtration, although for periods of about 1 to about 12 hours, which permit the handling of highly concentrated polymer solutions, preferably not more than 48 hours, in the 30 polymer solutions and which generally give good results for use. The solid complex avoids large volumes of washing liquid. In addition, filtration can also be used to isolate the subsequent pure isolation techniques from the sludge obtained. However, the development and refinement of these substances
it convenient to the sludge directly with the transition Another important feature of the mixing erfindungsmetallhalogenid is to form the method according to the active ₃₅ is that the Subject Author catalyst mixture. fending catalyst mixtures at elevated temperatures

The aluminum trialkyls are combined with the lithium temperatures to form solid, high-molecular, high-

hydride can be used to form the complex compound of recrystalline polymers,

sets that as a component of the catalyst while closely related mixtures of such poly

mixture is used. These aluminum trialkyls do not form 40 mers. For example, the reaction

are known and can by the formula AlR ₃ tion product of sodium hydride with a trialkyl

where R is an alkyl, preferably aluminum when used with a lower one

with 1 to 12 carbon atoms, in particular a transition metal halide, only liquid polymer

lower alkyl of 1 to 8 carbon atoms composed of propylene.

indicates. Suitable alkyls are methyl, ethyl, propyl, 45 which are used in the process according to the invention

Butyl, isobutyl, octyl, decyl, dodecyl. Aluminum-turned catalyst mixtures are extremely effective

trialkyle leading to the formation of white, crystalline, sam at elevated temperatures. The polymerization

solid complexes are used, which is a grain at temperatures in the range from 140 to 300 ⁰ C,

Form component of the catalyst mixture, preferably include in the range from 150 to 25O ⁰ C, through

therefore z. B. Trimethylaluminium, Triäthylaluminiüm, 50 led. At these high temperatures, the

Triisobutylaluminum, methyldiethylaluminum, Tril · · Catalyst generally in concentrations of

dodecylaluminum, trioctylaluminum or tridecyl- 0.01 to about 5 percent by weight, based on the

aluminum. The molar ratio of the organometal to be polymerized monomer, used, preferably

Lischen complex to the transition metal halide in wise in concentrations in the range of 0.1 to

of the catalyst mixture is based on the lithium 55 1.0 percent by weight. Lower catalyst concentration

content of the complex and can be used in the range of trations, but in general

0.1: 1 to 10: 1, preferably in the range of 0.5: 1, the speed of the polymer

up to 1.5: 1, fluctuate. formation very slowly, and with higher catalyst

The second component of the catalyst is a considerable difficult-to-halide concentration of titanium, vanadium, chromium, molybdenum 60 in controlling the reaction. The concentration and tungsten, the valence of the metal in general depends on the catalyst used this halide at least one less than that of the desired type of implementation, for example maximum Valence is. So are usually lower catalyst combination catalyst mixtures Compounds such as titanium ions used when higher yields of trichloride, titanium tribromide, vanadium tribromide, vanadium polymers per catalyst are desired. Other dintrichloride, Molybdenum dichloride, molybdenum trichloride on the other hand, high catalyst concentrations are or tungsten dibromide is used. Applies to most when high polymer yields per unit desirable results will preferably be reaction space. The ones at the high

7 8

Temperatures used according to the invention are easy to handle, as a result of which the deten polymers described here are highly crystalline, that is to say they have processes easily for a production in technical crystallinities of over 70, 80 or even 90%. Scale is suitable. The polymers obtained in carrying out the crystallinities of the products can be used by the invention to form extraction or X-ray diffraction techniques of films, molded articles or coated articles which are well known. Example to be used. The crystallinity of polypropylene-like substances can also be blended with other resin-like substances or with pigments, if the polymer is mixed in hexane at the back of the dyes, fillers or stabilizers, and the part of the solid polymer is allowed to boil.
which is insoluble in hexane at reflux, the crystalline io
Part is. example 1

The polymerization according to the invention is at

Pressures in the range from atmospheric pressure to As already stated, the forms by reaction

2000 atmospheres performed. Usually lithium hydride is formed with alkyl aluminum

Pressures of over 15 atmospheres, preferably in the 15 solid complex compound one component of a

Range from about 15 to 300 atmospheres, applied, active 2-component catalyst for polymer

in order to react sufficiently interesting for the practice of the named «-olefins to solid, high-

to get speeds. Higher pressures become molecular, highly crystalline polymers at high

then applied when the polymerization is in ab- temperatures. Such a complex is therefore produced

essence of a solvent is carried out. 20 put by adding a solution of 2.9 g of triethyl

In the absence of a solvent, the aluminum (0.025 mol) in 16 ml of heptane should be 0.4 g

weight of the gas present in the polymerization room, finely dispersed lithium hydride (0.05 mol) in 50 ml

add 1 to 4 times the weight of the already polymeric "mineral spirit". The mixture is 2 hours

ized product. This achieves long at 50 ° C under a dry nitrogen atmosphere

that the reaction mass remains so low in viscosity that it is stirred, a white sludge being formed. These

it is handled satisfactorily in the reaction space slurry is with 7.7 g of titanium trichloride (0.05MoI)

can be. Added to the formation of the active catalyst mixture by increasing the gas concentration,

in the reaction space not only the viscosity of the The catalyst mixture is in a dry

Reaction mass, but also a better heat 2-1 stirred stainless steel autoclave along with

transfer and a good catalyst distribution are 30 850 ml »mineral spirits« entered. The autoclave

possible. The gas that is sealed in is expediently flushed out with propylene and released

Reaction chamber is pressed in, heated from the to poly- 150 ° C. The propylene is stirring up

merizing monomers. 71 kg / cm ² pumped into the autoclave, and the

The polymerization reaction can be carried out in the presence of the temperature rises to 172 ° C. with a drop in pressure or the absence of an inert organic liquid. Propylene is then again run into the reaction medium. When the polymerisation vessel pumped to organization to the pressure of 71 kg / cm ^z, in the presence of an inert organic, liquid-realize. The reaction is allowed to run for 1 hour, this medium can proceed, and the autoclave will then be one of the inert organic liquids that is cooled and vented. The yield is 395 g of polypropylene not containing bound oxygen and the free 40 having an intrinsic viscosity of 2.07 (determined in Tetravon water, alcohol, ether or other connects hydronaphthalin at 145 ⁰ C), and a crystallizer endings are containing oxygen and the free nity of 92.6% (not extractable by normal from compounds with unsaturated bonds. Hexane at reflux).
The organic medium used can be an aliphatic

table alkane or cycloalkane, such as pentane, hexane, 45 Example2
Heptane or cyclohexane, or it can be a high molecular weight, liquid paraffin or a mixture of 230 ml of a 25% solution of triethylaluminum paraffins which are liquid at the reaction temperature minium, the 41.3 g of triethylaluminum (0.36 mol). It can also be an aromatic carbon equivalent, is added to 2.9 g lithium hydride (0.36 mol) hydrogen, such as benzene, toluene, xylene, or a 50 in 50 ml “mineral spirits”. The mixture halogenated "aromatic compound, such as chlorine is for 2 hours at 6O ⁰ C under Stickstoffatomobenzol be. Agitated a petroleum fraction of suitable sphere. The solid, crystalline complex boiling range obtained, such as odorless "mineral spirits" (a compound is put into a 317.97 dm ³ stirred vessel together with 56 g of titanium trichloride, paraffinic hydrochloride (0.36 mol) washed with sulfuric acid, substance, boiling point at 180 to 220 ⁰ C), especially 55 showed the 151.41 dm ³ "mineral spirits" contained. In the real good results. In addition, good results can be achieved. Propylene will be kept up to 32.5 kg / cm ^a when the polymerization is pumped into counter-pumping and stirring begins. The Polymeriwart of a dense gas, such as of highly compressed sationsreaktion is maintained at 150 ⁰ C., and propylene, throughput by operating at elevated pressure it seats 12 hours of continuous long. The concentration of being led. 60 polymers (based on the solvent) in the reaction

With the invention, a high-temperature poly- tion vessel is 18.0%.

merization process using a very tion, the catalyst is removed by filtration,

specific catalyst mixture is created, which is added and the filtered polymer solution is concentrated.

Formation of solid, high molecular weight, highly crystalline poly- The total yield of polymer is 29.484 kg

merers made of monoolefins with at least 3 carbons, 65 polypropylene or 287 kg per kilogram of catalyst.

Substance atoms can be used. The compo- The propylene has an intrinsic viscosity of 1.69

nents of the catalyst mixture are readily available (determined in tetrahydronaphthalene at 145 ⁰ C) and

Substances, and they have a crystallinity of 87.5% in the technical implementation

Although titanium trichloride is preferred as the transition metal halide, all can be lower valent Halides of molybdenum, vanadium, tungsten or chromium, preferably the chlorides of these metals, can be used in place of titanium trichloride with good results. So if transition metal halides, such as chromium trichloride, molybdenum trichloride, molybdenum dichloride, vanadium trichloride and tungsten trichloride, used in place of titanium trichloride in the above process results in polypropylenes ίο with crystallinities of over 85%. generally of over 90%

Example 3

A white, crystalline, solid complex is formed by adding about 0.4 g of lithium hydride (0.05 mol) in 100 ml "mineral spirits" 10 gTriisobutylaluminium (0,05MoI) and the mixture stirred at 6O ⁰ C for 2 hours . 7.7 grams of titanium trichloride (0.05 moles) is added to the slurry to form an active catalyst mixture. The catalyst mixture is diluted to 900 ml with "mineral spirits" and placed in a 2 l stirred autoclave. Propylene is pumped into the reaction vessel up to 71 kg / cm ² at 17O ⁰ C. After one hour, the autoclave is cooled, vented, and the propylene yield is 320 g. The intrinsic viscosity of the polymer is 1.75 (determined in tetrahydronaphthalene at 145 ⁰ C), and the crystallinity is 91.0%.

30th

Example 4

A 500 ml three-necked flask equipped with a stirrer and a thermometer tube is filled with 3.2 g of finely divided lithium hydride (0.4 mol), 50 ml of "mineral spirits" and 34.4 ml of a 25% solution of triethylaluminum, the 6th , 2 g of triethylaluminum is equivalent (0.54 mol) charged in a drying chamber filled with nitrogen. The mixture under nitrogen atmosphere for 4 hours at 6O ⁰ C stirred. The white flocculent slurry obtained is inputted together with 83 g of titanium trichloride (0.54 mol) into a stirring reaction vessel of 317,97dm ^3, 151.41 dm ³ odorless "mineral spirits" contains. Propylene is then pumped into the reaction vessel up to 29.0 kg / cm ² and stirring is started. The polymerization is adjusted to 156 ° C. and allowed to run for 12 hours. The polymer solution is filtered and concentrated, and the polymer is pressed out and granulated. A yield of 207 kg of solid polypropylene per kilogram of catalyst is obtained with a crystallinity of 85% (hexane extraction) and an intrinsic viscosity of 1.86 (determined in tetrahydronaphthalene at 145 ° C.).

Example 5

The lithium hydride - triethylaluminum complex is formed by adding 3.2 g (0.4 mol) of lithium hydride to 12.3 g of triethylaluminum (0.11 mol) and ^{stirring at 50 °} C. for 1 hour. This complex, together with 83 g of titanium trichloride (0.54 mol), gives a molar ratio of Li: Al: Ti of 0.75: 0.2: 1.0. This complex is introduced into a stirred reaction vessel of 317.97 dm ³ which contains 151.41 dm ^{3 of} odorless "mineral spirits". Propylene is pumped into the reaction vessel up to 29.0 kg / cm ² and stirring is started. The polymerization temperature is set to 158 ⁰ C. After 12 hours, the polymer solution is filtered and concentrated to remove the catalyst, and the polymer is pressed out and granulated. A yield of 473 g of solid polypropylene having a crystallinity (hexane extraction) of 85% and an intrinsic viscosity of 1.82 (determined in tetrahydronaphthalene at 145 ⁰ C).

Example 6

A suspension of 8 g of lithium hydride and 200 ml of n-decane is mixed with a solution of 57 g of triethylaluminum and 200 ml of n-decane. The mixture is heated and ^{stirred for 12 hours at 75 °} C. in an atmosphere of dry nitrogen to form a complex compound. 1.3 g of the complex are mixed with 1.5 g of titanium trichloride to form the catalyst slurry. This slurry is used to polymerize propylene at 160 ^° C. and 57.0 kg / dm ² . This gives 360 g of solid polypropylene having a crystallinity of 92% and an intrinsic viscosity of 2.1 (determined in tetrahydronaphthalene at 145 ⁰ C).

Comparative experiments

The unique nature of the catalyst mixtures used in the process of the invention is illustrated by the fact that neither lithium hydride nor trialkylaluminum is present in Combination with a low-valent halide is an effective catalyst mixture for polymerization of an α-olefin with at least 3 carbon atoms to form solid, high molecular weight, highly crystalline Form polymers at elevated temperatures. If propylene therefore using such catalyst mixtures polymerizing at high temperatures, the results are as follows:

Ver
search
No. Catalyst mixture
(molar ratios) catalyst
weight
G Polymes
temperature
⁰ C rization
pressure
kg / cm ² g polymer
per g of catalyst
per hour reason
viscosity Crystallinity
7o 1
2
3 5LiH: TiCl ₃
LiH: TiCl ₃
AlAt ₃ : TiCl ₃ 22.0
16.0
13.4 160
160
160 85
85
71 none
none
5 0.8 30th

A 2-component mixture, the lithium hydride or a trialkyl aluminum with the lower grade Transition metal halide, d. H. with titanium trichloride, is therefore not effective at high temperatures Catalyst only formation of solid, highly crystalline polymers from -olefins with at least 3 carbon atoms at high temperatures. In contrast, the complex reaction product that consists of Lithium hydride and trialkylaluminum is formed, extremely effective in forming solid, high molecular weight,

709 580/270

highly crystalline polymers from «monoolefins with at least 3 carbon atoms at high temperatures when using one of the halides mentioned of transition metals such as titanium trichloride is used according to the invention.

Claims (2)

Patent claims: 1. A process for the production of solid, high molecular weight poly - «- olefins with a crystallinity of at least 70% by polymerization of« monoolefins of at least 3 carbon atoms at a temperature of 140 to 300 ⁰ C, preferably 150 to 250 ⁰ C, and one Pressure from atmospheric pressure to 2000 atmospheres in the presence of a catalyst mixture made of a halide of titanium, vanadium, chromium, tungsten or molybdenum, in which the valence of the metal is at least one valence level below the maximum Valence, and a lithium-containing component, characterized in that one polymerizes in the presence of a catalyst mixture, the lithium-containing component from the solid reaction product of lithium hydride with an aluminum trialkyl, whose Alkyl groups preferably contain 1 to 12 carbon atoms, in a molar ratio of 1: 1 to 10: 1. 2. The method according to claim 1, characterized in that in the presence of a catalyst mixture, consisting of the reaction product of lithium hydride with aluminum triethyl or aluminum triisobutyl in a molar ratio from 1.5: 1 to 3: 1 and titanium trichloride, polymerized. Considered publications:
U.S. Patent No. 2,908,670. 709 580/270 5.67 ® Bundesdruckerei Berlin