DE1495611A1 - Process for the production of solid, crystalline poly-alpha-olefins - Google Patents

Description

Process for the production of solid, crystalline poly-A-olefins

The invention relates to a process for the production of solid, crystalline poly-olefins by polymerization of 4-olefins in the presence of a catalyst. In particular The invention relates to a process for the polymerization of propylene and its higher homologues in the presence of a new catalyst combination of unexpected catalytic Activity on products of unusually high crystallinity *

It is known that propylene and higher homologues can be polymerized in the presence of stereospecific catalysts to give solid, high molecular weight products of high crystallinity. A mixture of a transition metal halide and a suitable reducing agent can be used as the anionic catalyst. Such catalysts are, for example , in the

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Belgian patents 535,302, 534,792 and 534,888. It is also known to increase the stereospecificity of these catalysts by adding them another catalyst component «* ¥ -Sa? köl * H» g improved can be. Suitable catalyst components of this type are, for example, ethers, phosphines, phosphites, phosphates, phosphoramides, carboxylic acids, nitrogen »κ and Compounds containing sulfur, arsine, hydrogen antimony, hydrogen bismuth and the like. Catalysts containing such components are suitable as such especially for the production of solid, highly crystalline and high molecular weight polymers. In doing so, these increase Components both the stereospecificity of the catalyst system and the crystallinity of the polymerization product. On the other hand, however, their presence causes a considerable decrease in the activity of the catalyst system. This significantly reduces the yield of polymerization products per catalyst unit and time. In addition, such components can contain Catalyst systems generally only at relatively low levels Heating temperatures are used. you find primarily for processes that are used in the sludge phase be filled. In many cases, however, it is desirable to carry out the polymerization at temperatures which are high enough to keep the polymer liquid in a solvent or diluent. However, the catalysts known to date cannot operate at such high temperatures used.

■ M; ^; - ?. ·; * Ö «i47 / O870 bad original

The "invention was therefore the task of the main round, a ÜTerfalhreaa for the production of iron BoIy- ^ -olefiaem, in particular vaai polypropylene and hotter fol.y - ^ - olefliiieiL laÄer one clears crystallinity mx © aatfcwi © 1teelaa. ,, & ®s € © he jÄteile the ib'eteairmtem! traversing eaa nioiit mifwetst .. muesli © -S! © oat € r "& © FILLED of! catalyst be nOfeem" Male stereospeziflscn m, while oihne © ti vi * ty ms. "lose VSAA aaßerdem also Tsiei iemperaturen v" bar · ο "5μ" the hoeh are enough to DAB resulting Polymerieat in solvents or diluents to keep liquid.

This task was "by unwinding ^ ^ fel ottg a method solved is by eiehnet gekeamz _w € © ffl iman tie rPelymerisatijQn 4mete in the presence of Katalysatoirs teiHeahfSiirt ,,

1. a halide or a low-peptide 41lco3grt! A «! © Transition metals Tita ». ,, Zirfce-n ,, Vamatin ,, Chromium xDd« r Molylbdsn ,,

2. at least one of the following

a) a metal of Ia & roup, - II. -and- IIIa of perlodis-etojen system of ll ^ ementie, a <em IMiigrl # @ © Rivat hydride metals or -this fcompleaceaa JOJcaIialumlniamh, ydrid "

Td) an Or @@ E ^ i0 ⁱ * i4 & .li8i8niu.fflLi "EEHi" -H-al <© igieiELä. ^> d Aer SOrmel Ε, ΑΙοΧώ-,

E a «n laii & aserseiEL Mäcyl- _W <S ^ cl '©? AHJfcyl-, iEhenyl

X a

m imi. Vd tgamwe 2ts2aL <en Sübicwsl Umme € «ar W-erti ^ toeit & ess JOm-

bath

miniums or
c) a polymeric reaction product of aluminum and a methylene halide,

3. a Friedel-Crafts halide of an element of the groups II to VI or group VIII of the periodic table of the elements in complex with one of the stereospecificity of the catalyst increasing catalyst component.

The transition metal compounds suitable for carrying out the process of the invention consist of alkoxides, alkoxy halides and halides such as iodides, chlorides or bromides of titanium, vanadium, zirconium, chromium or molybdenum. Included the transition metals can be present in their maximum oxidation state or in reduced form. Titanium chlorides are preferred such as titanium tetrachloride, titanium trichloride and titanium dichloride are used. Other suitable metal halides and alkoxides are e.g. titanium tetrabromide, titanium tribromide, zirconium tetrachloride, Zirconium tribromide, vanadium trichloride, molybdenum pentachloride, Chromium tribromide, titanium tetrabutyoxide, vanadium triethoxide, Titanium tetraoctoxide, dichlorotitanium dibutoxide and the like.

The second catalyst component can be one of the following three Components include:

a) a metal such as sodium, potassium, lithium, magnesium, zinc, aluminum or the like., or. certain alkyl derivatives

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or hydrides that are metals such as sodium amyl, potassium butyl, Lithium propyl, aluminum triethyl, aluminum tripropyl, Aluminum tributyl, zinc dibutyl, zinc diamyl, Zinc dipropyl, ether magnesium bromide, sodium hydride, Calcium hydride, lithium aluminum hydride and the like, Id) an organoaluminum compound, such as ethylaluminum di Chloride, cyclohexyl aluminum dichloride, cyclobutyl aluminum dibromide, Ethyl aluminum dibrolide, ethyl aluminum aquichloride, Ethyl aluminum sesquibromide, dimethyl aluminum bromide, Propyl aluminum dichloride, dibutyl aluminum chloride, diethyl

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aluminum chloride and the like,

c) a polymeric reaction product of aluminum with a methylene halide such as ζ.Β »methylene dichloride. Such compounds are made by reaction of, for example, methylene bromide or Methylene chloride obtained with aluminum, and result in complex polymeric products of a structure that is not easily defined.

The third catalyst component is a Friedel-Crafts halide of the elements of groups II to VI or group VIII of the periodic table in a complex with a Catalyst component that enhances the stereospecificity of the catalyst system able to increase. Typical Friedel-Crafts halides that can be used to prepare this complex are Chlorides, bromides and iodides of beryllium, magnesium, zinc, boron, aluminum, silicon, germanium, tin, titanium, zirconium, Phosphorus, vanadium, chromium, molybdenum and iron. Suitable Friedel-Crafts halides are e.g. aluminum trichloride, Zinc dichloride, tin-IV-chloride, xthylaluminum dichloride, Diethyl aluminum monochloride, aluminum tribromide, beryllium dichloride, boron trifluoride, zirconium tetrachloride, titanium tetrachloride, Magnesium dichloride, ferric chloride and the like.

These Friedel-Crafts compounds are used in a complex with a compound which, if in freiber

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or non-complexly bound form in the catalyst system can be used to increase the stereospecificity of the catalyst. Such compounds are e.g. diaryl ethers such as diphenyl ether, bitolyl ether, dixylyl ether, Phenyl tolyl ether, di (biphenyl) ether, diphenylphenyl ether, Diethylphenyl) ether, di (propylphenyl) ether, di (n-butylphenyl) ether and the like. Preferably, a mixture of diphenyl ether known under the Kamen Dowtherm Biphenyl used. Also have the following

Complex-forming compounds proved to be suitable:

Amides such as _o Ι, Ν-dimethylformamide, acetamide, N, N-dimethylacetamide, propionamide and the like.

Ketones such as benzophenone, acetophenone, butanone and 3-pentanone. Carboxylic acid esters such as ethyl benzoate, ethyl malonate, butyl succinate, Propyl adipate, ethyl sebacate, butyl naphthoate and the like. Phenols such as p-cresol, o-ethylphenyl, m-propylphenol and others similar alkyl phenols. "

Compounds containing nitro and nitrile groups such as nitrobenzene, p-nitrotoluene, 2-kitro-p-cymol, benzonitrile, butyronitrile, Capronitrile, 2-kaphtholnitrile and the like. Sulfur-containing organic compounds such as dimethyl sulfoxide, Dimethyl sulfone, diethyl sulfate, N, N-dimethyl! Benzo1-sulfonamide, Dimethyl sulfoximine, dibutyl sulfoxide, dioctyl sulfone, Diphenyl sulfate, N, H-dipropylbenzenesulfonamide, diethyl sulfoxide and the like

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Organophosphorus compounds such as hexaalkylphoephoramides, Trialkyl and triaryl phosphates and irialkyl and triaryl phosphites have proven to be suitable reaction media or complexing agents such as hexamethylphosphoric acid triamide, Triphenyl phosphate, tricresyl phosphate, tridecyl phosphite, Triethyl phosphite, triphenyl phosphite, triethyl phosphate, Hexabutylphosphoric triamide, hexaoctylphosphoric triamide and the like. In the organophosphorus compounds, the alkyl radicals advantageously contain 1 to 8 carbon atoms. Also suitable are: primary, secondary and tertiary amines such as trialkylamines, e.g. triethylamine, tributylamine, trihexylamine as well as triarylamines such as triphenylamine; Onium compounds of nitrogen, phosphorus and sulfur such as = tetrabutylammonium iodide, tetramethylphosphonium bromide, Triethylsulfonium iodide}

Tetraalkylureas and tetraalkylthioureas, such as, for example, tetramethyl urea, tetrabutylurea, tetraethylthiourea; Metal salts of carboxylic acids, for example sodium benzoate, calcium malonate, calcium eucinate, borium adipate, zinc eebacate, lithium naphthoate, and the like;

Oxides and alkoxides of the metals of groups I and II of the periodic table, such as sodium oxide, potassium oxide, lithium oxide, calcium oxide, magnesium oxide, barium oxide, sodium methylate, potassium butylate, lithium ethylate, calcium propylate, magnesium penty-

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lat, barium hexylate and the like;

Alkoxides of transition metals, such as jjf / ί titanium tetrabutylate, Zirkontetraäthylat, Vanadintetramethylat and the like.} Alkali metal fluorides such as sodium fluoride, potassium fluoride, lithium fluoride and trialkyl and triarylarsines or trialkyl and Triarylstibine such as Triäthylarsin, tributylstibine, triphenylarsine, triphenylstibine.

The complex used as the third catalyst component can can be represented by the formula MXZA, where:

MX a Friedel Orafts * halide as above,

M is a metal from group II big 71 or VIII of the periodic table,

X is a halide,

_{n is} an integer of the same size as the valence of M, A is a compound that increases the stereospecificity of the catalyst,
Z is an integer from 1 to 6.

_{The process of the invention can be preferably m} in the liquid phase in the presence of an inert organic carrier liquid

wise an »inert liquid hydrocarbon, carried out /.

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But it can also be carried out in the absence of an inert diluent. At temperatures of 50 to 25O ⁰ C, particularly good results can be obtained. The reaction is preferably carried out at temperatures of 50 to 150 ° C. The pressure can be between atmospheric pressure and very high pressures up to about 1,410 kg / cm. A particular advantage of the invention is the fact that pressures of about 2.10 to 70 kg / cm also give excellent results. Thus, extremely high pressures, as they have been required since then, are not necessary. The liquid carrier to be used is expediently one which forms an inert liquid reaction medium.

The method of the invention is particularly useful for the production of highly crystalline polypropylene, polybutene and Suitable for polystyrene. However, ethylene and ethylene propylene mixtures and other CL monoolefins can also be used with the same success are polymerized with preferably up to 10 carbon atoms. The manufacture according to the method of the invention

s bare polyethylene has a softening ^ (softening or fusion) point of about 120 ⁰ C. The products produced from this material can therefore be brought into contact well with boiling water without showing thereby to deform or other adverse effects. According to the process of the invention, solid polymers with molecular weights of

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more than 1,000, in particular more than 10,000, can be produced. Polymers with molecular weights of 1,000,000 and higher are also easy to prepare. The high molecular weight polyethylenes which can be prepared by the process of the invention have a high density and are insoluble in solvents at normal temperature. At temperatures above 100 ⁰ O, however, they dissolve in solvents such as xylene, toluene or tetralin. This characteristic solubility makes it possible to keep the polymer in solution in the reaction medium during the polymerization process and to precipitate it therefrom by lowering the temperature.

The catalyst used in the process of the invention is particularly suitable for the polymerization of propylene to high density crystalline products. The polypropylene that can be produced has a softening point above 155 ^° C. and a density of 0.91 and higher. The density of polypropylene is generally on the order of 0.91 to 0.92.

The polyolefins which can be produced by the process of the invention can be deformed or extruded. They can be processed into sheets, sheets, foils and other molded articles which have a greater rigidity than the corresponding high-pressure polyolefins. The products can be made into tubes or hoses of excellent strength .extruded and processed into many objects by injection molding

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The polymers can also be drawn cold into strips, ribbons or threads of high elasticity and strength. In addition, threads of high strength can be spun from the molten olefins.

The temperature to be used in the polymerization is limited by the decomposition temperature of the catalyst. In general, temperatures between 50 and 250 ^° C. can be used. Normally, it is not practical or economical to carry out the polymerization at temperatures below 50 ⁰ C. The process can be well controlled at temperatures not significantly higher than room temperature. This is advantageous in terms of operational production. The pressure can be chosen so high that the reaction mixture is just liquefied during the polymerization. If necessary, however, higher pressures can also be used. The pressure is generally achieved by forcing on the monomer, with additional monomer dissolving in the carrier medium as the polymerization progresses.

The process of the invention can be carried out batchwise or continuously. Because of economical reasons a continuous process is appropriate. In particular

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will give good results if the process is continuous. achieved when a polymerization mixture is more constant Composition continuously brought into the polymerization zone and the resulting polymer at an equivalent rate is removed from it again. The relative concentration of the various components remains in the Polymerization zone fairly constant during the reaction and the polymers show up within a relatively narrow range Area has an extremely uniform molecular weight distribution. Since such polymers do not have any significant or particularly high contain low proportions, they are superior to the products that can be produced by batch processes.

In order to achieve the greatest possible uniformity of the polymer, the temperature is increased in a continuous process expediently kept constant within the desired value. Since / it is advantageous that the monomer as possible is concentrated, the process is expedient at

Pressures from 2.10 to 70 kg / cm of the monomer are carried out. The quantity ratio of carrier material, monomer and catalyst mixture can be varied widely. A catalyst concentration of 0.1 to 28 w .- # based on the carrier medium e.g. delivers the best results. The concentration of the monomer in the carrier medium can be very different and depends on the reaction conditions. It is generally between 2 to 50 wt. #. For one in the liquid phase

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procedures carried out the concentration of the monomer 2 to 10 wt. -i "based on the carrier medium, while in a running in the slurry phase process, higher concentrations of the monomers, for example $ 40 or more are appropriate. Higher concentrations of monomers generally increase the rate of polymerization, but it is advisable not to use more than 5 to 10 revr.-fo of monomers for processes in the liquid phase. Otherwise the polymer dissolved in the reaction medium would form a very viscous solution.

Advantageously, approximately the following molar ratios are selected in terms of order of magnitude;

Molar ratio of component 2 to the transition metal compound between 1s0.5 to 1: 2, ·

Molar ratio of component 2 to the one Friedel-Crafts catalyst containing complex between 10: 1 to 1: 5, but the molar ratios can also be above or below. The polymerization time can vary widely. In the case of batch processes, it is generally between 30 minutes polymerized for up to several hours. Will the polymerization carried out in an autoclave, contact times of one to 4 hours may be required. With continuous The contact time in the polymerization zone can be as desired can be varied. Be * circulation procedures are contact pages

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More than half an hour to 1 hour is usually unnecessary. File wir4 the polymer precipitated, carrier medium and unreacted Catalyst go back to the feed zone where the catalyst replenishes and additional monomer is added will.

The organic carrier medium can consist of an aliphatic alkane or cyeloalkane such as pentane, hexane, heptane or cyelohexane or a hydrogenated, aromatic compound such as tetrahydronaphthalene or decahydronaphthalene, a high molecular weight liquid paraffin or a paraffin mixture which is liquid at the reaction temperature. Furthermore, aromatic hydrocarbons such as benzene can consist , Toluene, xylene and the like or halogenated aromatic compounds such as chlorobenzene, chloronaphthalene or orthodichlorobenzene can be used. There are many possible variations with regard to the carrier medium. In any case, the carrier medium used should be liquid and relatively inert under the given reaction conditions. Preferably, hydrocarbons are used other solvents such as ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene _f mono- and dialkylnaphthalene, n-pentane, n-octane, isooctane, methylcyelohexane, tetralin, decalin and an their known, inert hydrocarbons are suitable. It has proven to be useful to add the diluents before they are used in the polymerization

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Vf -

clean. For this purpose, the solvent can be brought into contact with the polymerization catalyst in a distillation process or in some other way so unwanted traces of impurities are removed. The catalyst is preferably previously with the to polymerizing α, mono-olefin brought into contact.

The polymerization can be carried out simply by combining the components of the reaction mixture without additional heating. Only if elevated temperatures are required to increase the solubility of the polymer in the carrier medium does it have to be heated. When producing particularly uniform polymers by using continuous processes which proceed with relatively constant proportions, it is advantageous to keep the temperature constant within a relatively narrow range. Since the percentage of liquid carrier in the polymerization mixture is very large, the temperature can through. Heating and cooling of the vegetables can be easily regulated.

example 1

In a dry box filled with nitrogen, in a well-dried 250 ml bottle, 200 ml of toluene and 21.3 g

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given sublimed aluminum chloride. While turning the bottle, 28.7 g of hexamethylphosphoric triamide are added (HPT) added slowly. After adding the last drop of HPT all aluminum chloride is in solution. The solution is now cooled to room temperature and until the make topped up with dry toluene. The solution obtained contains 0.02 g of aluminum trichloride. HPT per milliliter.

100 ml of toluene and 0.5 g of a catalyst mixture of diethylaluminum chloride and titanium trichloride in a molar ratio of 1: 1 were added. Then will 28 ml of the aluminum trichloride HPT solution were added. The bottle is placed on the shaker with a propylene

Pressure vessel of 2.10 kg / cm connected. After commissioning of the shaking, the temperature is brought to 70 ⁰ C. The rate of polymerization is 50 g per hour. As soon as the pressure drop during the reaction has reached 0.21 kg / cm, the valve to the pressure vessel is opened and

the pressure increased again to 2.10 kg / om. After 6 hours it will one calculated by adding up the individual pressure core requirements Total pressure drop registered of 13.02 kg / cm. This pressure drop corresponds to a theoretical yield of 93.5 g Polymers. The yield is 89.6 g. The polymer was 93? 6 crystalline. Another attempt is made for comparison

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J?

carried out without the addition of ΑΙΟΙ, -ΗΡΤ. The rate of polymerization is only 7 g per hour and the polymer is only 85 $ crystalline. Will the trials with Ethylene carried out, so occurs in terms of the rate of polymerization the same effect on. When using 1-butene, there was a corresponding improvement with regard to the rate of polymerization and the crystallinity found in the presence of the AlCl, -HPT complex.

Example 2

In a corrosive autoclave, 0.45 g of ethylaluminum dichloride, 0.55 g of titanium trichloride and 0.9 g of a complex of zinc dichloride and hexamethylphosphoric acid triamide (Zinc dichloride x 2 HPT). The autoclave is filled with 200 ml of liquid propylene and attached to a shaking machine connected. The temperature is brought to 85 ° C. and the autoclave is shaken for 4 hours. After completion After the experiment, the autoclave is cooled, ventilated and opened. A yield of 88 g of polypropylene, 97% of which is crystalline, is obtained is. For comparison, a further test is carried out without the addition of zinc dichloride · 2 HPT. This forms an oil mixture. Corresponding results are obtained when instead of zinc dichloride. 2 HPT a tin chloride / sodium fluoride complex (Tin tetrachloride x 2 sodium fluoride) is used.

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Example 5

A 500 ml autoclave is charged with 100 ml toluene, 0.13 g aluminum powder / 0.88 g titanium tetrachloride and 1.4 g of a complex of aluminum trichloride and hexamethylphosphoric triamide (AlCl ₃ · HPT) and transferred to an ethylene pressure vessel of 2.10 kg / cm connected. The mixture is shaken on a shaker and the temperature brought to 8O ⁰ C. As soon as the temperature becomes constant, the pressure drops. Every time the pressure drops by 0.21 kg / um, the valve to the pressure vessel is opened in order to increase the pressure again to 2.10 kg / cm. The pressure drop results in a polymerization rate of 18 g per hour. The reaction is terminated after 4 hours and the polymer is isolated. The yield is 70.6 g of polyethylene. The product does not contain any components soluble in acetone. For comparison, another test is carried out without aluminum trichloride · HPT. Here, an induction time of 70 minutes is required before eintf Alöi ^ ken äes Ärückes occurs. The polymerization rate "is 8 g per hour.

With a reaction time of 4 hours, the polymer

extracted according to sation product with acetone. 2.6 g sx & xr are obtained

one
$ 8.1 oily fraction. Corresponding results are obtained if instead of aluminum trichloride ° HPT complexes such as ethylaluminum dichloride and triphenylphosphine (C ₂ H

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to

or diethyl aluminum chloride and calcium oxide can be used.

Example 4

3-Methyl-1-butene is polymerized according to the method described in Example 3. A tin chloride / diphenyl ether complex (SnCl. · 2 (CgH ₁ -) pO) is used for this. After 4 hours, 91 poly-3-methyl-i-butene are obtained. The polymer is crystalline to the extent of 98%. *

Example 5

Butene-1 / is polymerized according to the method described in Example 3. The catalyst component aluminum trichloride · HPT is, however, replaced by an aluminum tribromide sodium acetate complex (AlBr ₅ -CH ₅ COONa). A temperature of 85 ^° C. is also used. 89 g of a product which is 96% crystalline are obtained. Corresponding results are obtained with a beryllium dichloride / hexamethylphosphoric acid triamide (BeCl ₂ ^{# HPT) complex.}

Example 6

The procedure described in Example 3 is repeated with styrene. After 4 hours, 90 g of a high-critical

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Stable polystyrene ^ In the same way, 3-methyl-i-buty1-methyl-i-pentene, allylcyclohexane and 3-methyl-1-ii63EOft can also be polymerized to form highly crystallized products. If the aluminum complex by HPT Bertrifluorid / diphenyl ether ₍₂ ⁰ PO (OG ₂ H ₅₎ ZnGl,) replaced (BF * (C ₅ H _{5) 2/0)} or zinc dichloride / Triäthylphäsphat, we obtain the results thereof,

Example 7 *

The procedure described in Example 3 is repeated with butadiene. As a complex of zirconium tetrachloride and titanium tetrabutoxide (ZrOl, · Ti (OBuy ^) is used. After 4 3 ^{do (s} yield is 85 g PolyMtadien.

Example 8

For the production of polyisoprene, isoprene is used according to the method of Example 3 in the presence of an aluminum tri-taromide / Titanium tetrabutylate complex (AlBr ^ -Ti (OBu)) polymerized.

⁵ 4 Similar results are obtained with complexes of titanium tetrachloride and hexamethylphosphoric _{acid triamide 4} nesium dichloride and dimethyl carbonate (MgCl ₂ DMF) or from iron chloride and hexamethylphosphoric acid triamide (FeOl ^ HPT).

ti

Some of those used in complex with Friedel Grafts Halides Compounds were used as catalyst components to increase the stereospecificity of the catalysts. However these components generally have the unpleasant property, the reaction rate of the catalyst to reduce. The invention is based on the surprising finding that when these components together with Friedel-Crafts catalysts are used .. excellent * ^ Compounds to increase the stereospecificity of the catalyst arise which reduce the reaction rate of the catalyst not reduce. This enables extremely economical polymerization reactions.

Example 9

To illustrate the advantages of the new catalysts different catalysts are compared with one another for the polymerization of propylene. Be with every attempt 0.51 g of titanium trichloride used. The implementation is as follows carried out: In a sack box flushed with nitrogen 100 ml over sodium in a 250 ml Pyrex pressure bottle The pressure bottle is then given a magnetic stirrer and a Provide a suction valve, take it out of the dry box and connect it to an ethylene pressure vessel *! » Seed the bottle

is flushed through with highly purified propylene, propylene is introduced under a pressure of 0.70 kg / cm. The reaction mixture is kept ^{at 70 °} C. by means of a thermostatically controlled silicone oil bath. The polymerizations are terminated after 1 hour. The results are compiled in the following table.

Catalyst activator reaction properties of the

speed of polymers ₀ (activity) crystallinity Mmole / L / sec. (η) $>

(C ₂ H ₅ ) ₂ AlCl / TiCl ₅
(C ₂ H ₅ ) ₂ AlCl / TiCl ₅ HPT ³ 0.423
0.287 1.82
2.88 88.7
92.Ο (C ₂ H ₅ ) ₂ AlCl / TiCl ₃
(C ₂ H ₅ ) ₃ Al / Ti01 ₃ . HPT ⁰ AlCl ₅ 0.595
1.62 5.01
1.84 93.0
80.5 (C ₂ H ₅ ) ₃ Al / TiCl ₃ (C ₆ H ₅ ) ₂ O ⁴ 1.18 2.49 86.0 (C ₂ H ₅ ) ₃ Al / Ti01 ₃ - (G ₆ H ₅ ) ₂ Ö-
AlCl ₃ 1.49 2.61 92.0

1) Used in a molar ratio of 0.4 based on titanium trichloride,

2) based on the percentage of hot methyl isobutyl ketone insoluble polymer,

3) HPT = Hexamethyl-lphosphortriaiaid,

4) (C ₆ H ₅ J ₂ O = diphenyl ether.

Many anionic catalysts for olefinic polymerisation Hydrocarbons are mainly used in reaction

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suitable in the mud phase. The in this procedure The low temperatures necessary for optimum catalyst reaction are not sufficient, the resulting polymer in the Dissolve reaction medium. If catalysts are used in the polymerization, according to the invention in the Component 3 together with Friedel-Crafts Ha ^ ogeniden complex however, the temperature cannot be increased. However, it has now surprisingly been found that carry out the polymerization reactions in the presence of the third complex catalyst component also in the liquid phase permit. Reactions that take place in the liquid phase are preferred to those in the sludge phase because of the reaction conditions can be chosen so that the polymer formed dissolves in the diluent or solvent and can thus be easily separated from catalyst residues. The fact that the polymerization reaction is in the presence of the catalyst according to the invention can be carried out in the liquid phase and thereby a polymer of essential higher crystallinity results than in all previous processes is astonishing and shows the unexpected increase the stereospecificity of the catalyst at these relatively high temperatures.

The following examples demonstrate the benefits of the present

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β e * s-

of

In fItta-Mf © ir

dei * l # fii | $ S # § Trending Yerfah * © Ä

This example shows #ie high

plexen Aktivator®

Results that are achieved by adding a com will

CanT At JMeli i # r fölgen # eGi Msitae 0.51 g of trichloride zT * fe: s # fi1 * Is wi # i #ie fölft 'proceed: In a with $ ti # Äö> föff gesfüi-leia TroökenTäox a sion-stableF Steel autoclave with 150 ml of dry mineral spirit and aem catalyst legöhiökt »The a ^ oklav is closed, from the irockenl © * giBOmmeh and to the Sehttttelmasöhine gölÄoht« Dana, © »§ © ml of liquefied i ^ ofylene is introduced, the old autoclave wlti afaöoh to 135 ⁰ C. The polymerization time is 4 hours. The results are summarized in the following Talelle susii "ftf" J

Used latäly ^ a & gewan sator vator *

HPf ^J HPT * AlCl,

- Properties of the poly

Iristallinity

Or) *

1.32
1.75
1.71

79.5 86.3 92.7

- - 2fr ~

t) Mo ratio used 0.4 based on titanium trichloride,

2) based on the percentage of hot methyl isotatyl ketone insoluble a polymer! sat,

3) HPT = hexamethylphosphoric triamide.

With this invention, polyolefins such as polypropylene can be easily produced by using a combination of catalysts with unexpectedly improved effectiveness. The polymers can be extruded, mechanically comminuted, cast or shaped. The polymers can be used as additives to relatively more flexible polyhydrocarbons to products with any desired combination of properties _. Pigments and the like, as well as waxes and the like with other polymeric materials.

The foregoing has shown that a catalyst not previously used in such technical processes is used in this polymerization process * By using this new catalyst, it is possible to produce polymerized hydrocarbons, in particular polypropylene, with properties that have not yet been achieved. Since, for example, the polypropylene polymerized in the presence of the catalyst combinations of our invention does not contain any rubber-like products _? are

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Extraction processes not required. In addition, the polypropylene made by the process of the invention possesses high crystallinity, an unusually high softening point and an exceptional thermal stability. As a result of the unexpectedly high crystallinity, this polypropylene is very stiff and differs from the previous technically produced polymers due to their excellent characteristic properties.

The catalysts described are generally suitable for the production of high molecular weight, crystalline hydrocarbons. When the polymerization is carried out in the presence of hydrogen, the molecular weight can largely can be varied. The hydrogen can be introduced alone or together with monomeric olefin. The after Polymers that can be prepared by the process of the invention can be prepared by suitable extracting processes, e.g. by washing out be freed from the catalyst with water or lower aliphatic alcohols such as methanol.

Although those applicable to the method of our invention Catalyst combinations are mainly used for the polymerization of οί-monoolefins, their applicability is not limited only to monoolefins, but other oC-olefins such as butadiene, isoprene, 1,3-pentadiene and the like can also be used. are polymerized.

ν 9098A7 / 097 0

Claims (2)

14956m claims 1. Process for the production of solid, crystalline poly-olefins by polymerization of <£ -01efinen, in particular of propylene and propylene-butene-1 mixtures in (presence a catalyst, characterized in that the polymerization is carried out in the presence of a catalyst, consisting of 1. a halide or a lower alkoxide one of the Transition metals titanium, zirconium, vanadium, chromium or molybdenum, 2. at least one of the following a) a metal from Group Ia, II and IHa of the Periodic Table of the Elements, an alkyl derivative or hydride thereof Metals or a complex alkali aluminum hydride, b) an organo-aluminum halide of the formula R ₃₁ AlX _n or R, AIpI ,, in which: R is a lower alkyl, cycloalkyl, phenyl or tolyl red, I a chlorine or bromine *, m laid η integers whose sum of the valence of the aluminum corresponds to or c) a polymeric reaction product of aluminum and a Methylene halide, 3ο a Friedel-Crafts halide of an element of the groups II to VI or group VIII of the periodic table 909847/0970 H95611. Elements in complex with one of the stereospecificity of the Catalyst-increasing catalyst component. 2. The method naoh claim 1, characterized in that one For the production of polypropylene, the polymerization is carried out in the presence of a catalyst consisting of ethylaluminum dichloride, titanium trichloride and a complex of aluminum chloride and hexamethylphosphoric triamide. 3 · The method according to claim 1, characterized in that for the production of polypropylene dLe polymerization in the presence of a catalyst consisting of metallic Aluminum, titanium tetrachloride and a complex of aluminum aluminum dichloride and hexamethylphosphoric acid triamide 4. Process according to claim 1, characterized in that for the production of τοη polypropylene the polymerization φ in the presence of a catalyst, consisting of ethylaluminium dichloride, titanium chloride and an inta complex of diethylaluminum chloride and calcium oxide. 5. The method naoh spoke 1, characterized in that the polymerization in Qe is used for the production of polypropylene BATH ORIGINAL presence of a catalyst consisting of metallic aluminum, titanium tetrachloride and a complex of tin-IV-chloride and diphenyl ether. 6. The method according to claim 1, characterized in that for the production of polypropylene, the polymerization is carried out in the presence of a catalyst consisting of metallic Aluminum, titanium tetrachloride and a complex of aluminum tribromide and sodium acetate.