DE1645284A1 - Process for making polyolefin products - Google Patents

Description

Description of the patent application

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ N.V. 30, Carel van Bylandtlaan, Hague, The Netherlands

concerning

Process for making polyolefin products

The present invention relates to the manufacture of polyolefin products, either in the form of molded articles (which are used as articles of manufacture, for example as molded articles, extruded Tube and film are designated), or in j? Orm of polyolef ^ solid particles, for example Pellets or chips (nibs) are used as the starting material for the production of such shaped Objects can be used. The present invention also relates to those made therefrom molded articles and polyolefin solid particles.

The Ziegler process for the production of polyolefins the homopolymers, e.g. B. polyethylene and polypropylene,

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or mixed polymers, ζ. B. ethylene or propylene copolymerized with smaller amounts of one or more olefinic or diolefinic monomers, are well known now. So far it has been considered necessary to use a Ziegler-made polyolefin subject to intensive cleaning in order to remove the catalyst and / or decomposition products from it, which have been trapped in the solid polyolefin, which is suspended in the liquid diluent phase

"forms as the polymerization proceeds.

Many proposals have been made for performing such cleanings. However, it can be said generally that it is common practice in Ziegler polymerization to remove the solid polyolefin from the "work up" the sludge obtained from the polymerization reactor, by first decomposing the active catalyst in the slurry and in the polymer itself by adding an alcohol together with optionally

I a certain amount of a mineral acid to that

Polyolefin pulp and then exhaustively the catalyst residues from the polyolefin by intensive. ', Ash extracted with aqueous washing liquids. The polyolefin obtained is finally separated by filtration or centrifugation, yielding a reuchtes olefin product that contains a substantial 'Jassermenge which must be removed by irocknen prior to processing of the polyolefin to solid forms, such as chips or pellets, which it for

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Supplying the plastics industry as raw material for the production of molded objects' is suitable.

It has now been found that this expensive work-up can be avoided provided that the polymerization is carried out under certain conditions, as described below, which is a polyolefin yield per unit weight of catalyst which is so much larger than that which is obtained when polymerizing under normal conditions, ' which have previously been considered essential for the Ziegler process, that the amount of Catalyst residues in the polyolefin product, for example, at most after a simple separation of the pulp of the liquid phase from the polymerization reactor is negligible for many purposes the polyolefins needed in the plastics industry are negligible.

According to the invention, a method for producing a polyolefin product, which is a molded article, (as defined) or polyolefin solid particles that for use as an initial Cleaning) for such research objects in cfer plastic Industry is likely to be carried out by one Olefin or a mixture of olefins in a reaction mixture which contains a dispersion of a Ziegler catalyst in liquid i-hase that contains a mixture (a) of a

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Compound of a metal of the group, wherein the metal is present 4A ₁ 5A or 6A of the Periodic Table in this connection in one valence state, the lower _a ls the normal maximum valency of the metal, and (b) an organometallic compound of a metal of Group IA, 2B or 3B of the periodic table, is polymerized under polymerisation conditions which allow the maintenance of a concentration of the group 4A, 5A or 6A metal compound in

Allowed the reaction mixture, so that the Konzentrais.-.

tion of the chemically bound Group 4A metal, 5A or 6A under 0.15 millimoles of metal per liter is in the liquid phase of the reaction mixture, from the reaction mixture solid polyolefin and without prior dry cleaning around either a molded one Article or polyolefin solid particles to form, holds in a heat-plasticized state.

During the Ziegler catalyst, any catalyst from any metal compound (or compounds) of the group 4A, 5A or 6A, which, in the concentration used, can catalyze the olefin polymerization or interpolymerization, are particularly suitable Catalysts those formed from group 4A metal compounds (especially titanium compounds) and those from group 5A (especially vanadium compounds). Especially among such

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suitable catalysts, those made from vanadium compounds are described as particularly advantageous for polymerization plants which the size of the polymerization reactor plays an important role, as determined according to the invention it has been found that particularly high rates of polymerization together with high polymer yields per unit weight Catalyst at very low vanadium concentrations can be obtained with such catalysts. On the other hand are made of titanium compounds prepared catalysts are quite suitable for carrying out the process according to the invention in Polymerization plants in which fewer restrictions apply to the size of the polymerization reactor will. Examples of vanadium compounds that can be used to make such Catalysts are vanadium tris (acetylacetonate), vanadiumoxy bis (acetylacetonate), sec. Butyl vanadate, VO (OBu) -., Also called Vänadiumoxytris (isobutoxide) can be called the vanadium complex of diisopropylsalicylic acid (commonly referred to as vanadium · diisopropyl salicylate), vanadium oxytrichloride and vanadium naphthenate. While compounds of metals of group 5A, and 6A (e.g. chromium compounds such as chromium acetylacetonate) can be used, as well such as compounds of Group 4-A metals in manufacture of the catalysts to carry out the Brfin-

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dung, are catalysts made from vanadium compounds, including vanadium compounds, the complexes aromatic hydroxy or mercaptocarboxylic acids (preferably with a carbon substituent or Substituents in the molecule) or the hydrocarbon-soluble vanadyl salts of organic acid, including the sulfonic acids, often preferred from the standpoint of the possibility of using smaller polymerization reactors. In this way the present delivers Invention a considerable technical advance, since it enables the capacity of an existing one Ziegler polymerisation system to be increased considerably.

In general, the amount of catalyst in the practice of the present invention is preferably so large that the concentration of chemically bound metals of group 4A, 5A or 6A in the reaction mixture, below 0.1 millimoles of metal per liter of liquid Phase of the reaction mixture is maintained. The optimal one Catalyst concentration is generally-of the individual group 4A, 5A or 6A metal compounds present and can easily be determined by experiment

i. - = ■

[to be determined. For example, for the preferred Group 4A metal, namely titanium, a concentration between 0.01 and 0.08 millimoles of titanium per liter preferred and for the preferred metal of Group 5A, namely vanadium, a concentration between 0.0005

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and O ₁ oil millimole vanadium per liter «

While the use of halogen-containing organometallic compounds is not excluded, preferably the organometallic compounds in the catalyst contain a compound or compounds which do not contain halogen in the molecule. For example, in the case of an organometallic compound of a group? B metal, a compound having not more than one halogen atom per molecule may be used. In such a case, the halogen may be iodine, although chlorine and bromine are not excluded. It is therefore not excluded that this compound of a Group 4A, 5A or 6A metal may itself be prepared under conditions including the presence of halogen, e.g. B. chlorine, which can react with a halogen-free organometallic compound to give a halogen-containing organometallic compound, although in this case the amount of halogen so reactive will generally be less than the amount that is on a stoichiometric basis with the total amount of the halogen-free organometallic compound can react in the catalyst system. Optionally, the metal compound of Group 4A »Ί 5A. or 6A can be prepared under conditions that the amount of the reactable halogen is small and / or the compound can be free or almost completely free of halogen

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getting washed. ~

The use of a Zleg ^ er catalyst from a organometallic compound that has no halogen or only a small amount of halogen in its molecular structure has an advantage that a reduction in the amount of halogen impurity in the polyolefin obtained is made possible. Such organometallic

'Connections, e.g. B ,. Aluminiumtrialkyls, Aluminiumalkylhydride and ^A luminiumalkylalkoxyde are of course as a suitable metal · Organ compounds for preparing Ziegler catalysts. While it may be advantageous in certain circumstances to use an organometallic compound, e.g. B. to use an Og or higher aluminum trialkyl, or a mixture of alkylenes, which are sufficiently stable with regard to its co-catalytic effectiveness, when it is in the form of a Ziegler catalyst to give a Ziegler catalyst a considerable) life , so this need not be essential and it may be more advantageous to use an active but relatively short-lived alkyl such as aluminum triethyl, since it is always possible to compensate for the loss of organometallic constituent by adding adequate fresh alkyl to the reaction mixture in the course admits the reaction. Examples in the broader definition above of organometallic compounds which can be used to prepare catalysts for carrying out the present invention are the alkyls,

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Cycloalkyls and aryls of metals, for example aluminum, zinc, magnesium, calcium, strontium and lithium, the alkylalkoxides and arylalkoxides (and corresponding aryloxides) of the metals of groups 2 and 3, the alkyl hydrides of these metals of groups 2 and 3 and their alkyl halides which are not contain more than 1 halogen atom per molecule. From these organometallic compounds, the metal alkyls and cycloalkyls with only one alkyl or cycloalkyl group can be excluded for special considerations, including those metal alkyls and cycloalkyls, but in particular the alkyls which contain alkyl or cycloalkyl groups, each with at least 6 carbon atoms, for example more than 10 carbon atoms Mixtures of such alkyls and cycloalkyls can be used, for example a mixture of two or more alkylenes with alkyl groups having a number of carbon atoms in the range from O ₁₀ to O ₂ Q, for example O-rp or C-,. to 0-, g.

In the case of the preferred Group 4A catalysts, for example, the catalyst is usually prepared as a titanium trihalide, usually a trichloride such as β- or χ -titanium trichloride, although many other compounds of the Group 4A metals _f 5A or 6A are used to make the catalysts for practicing the invention are suitable. However, it has been found according to the invention that in terms of the very low

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Amount of transition metal compound in the process of the present invention (as indicated by the maximum concentration of 0.15 millimole of metal per liter of the liquid phase of the reaction mixture) the use of a Group 4A, 5A or 6A metal halide only introduces very little halogen into the system, and is commonly produced β- or \ K-titanium trichloride, accordingly a preferred Group 4A compound in preparing the catalyst for operation of the present invention.

In the case of the catalysts made from a Group 4A metal compound, the Concentration of the catalytic transition metal that is maintained in the polymerization mixture as the group 4A metal content of the liquid phase This mixture expressed in the range of 0.02 to 0.08 or 0.1 millimole of metal per - "iter, e.g. approximately 0.05 millimole per liter. General upkeep a concentration represented by a maximum of 0.1 minimol per liter and a minimum of 0.01 millimole of metal per liter ensures that im In the case of a titanium catalyst, the yield of polyolefin

i (per unit weight of catalyst metal), which can be obtained when polymerizing in the manner of the invention, is high enough to avoid the need for purification.

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'As stated above * you can even use smaller amounts of Vanadium catalysts are required to obtain similarly high polyolefin yields. It is surprising that very high yields are obtained can, with a heterogeneous Ziegler catalyst, since it previously appeared as if the polymerisation mechanism was based on the growth of the polymer chains the active sites of the catalyst sites borrowed influenced inclusion of the catalyst in the polymer product leads when the polymer product turns into a solid the reaction mixture forms and that the enclosed Catalyst becomes inactive * as a result of its physical inaccessibility to the olefin monomer. Because consequently the Feetetoffcomponent of a heterogeneous Zi ■ gler catalyst from a transition metal compound of the Ziegler catalyst is formed and includes these should be expected to include this Vüse an extremely high metal content in the polyolefin product contribute and the permanent renewal of the transition metal compound in an active and monomer accessible Make form necessary in the action deletion. Indeed However, it has been found according to the invention that, surprisingly, a certain amount of Ziegler catalyst can be used to catalyze the formation of a much larger amount of polyolefin than it seemed possible up to now and that this can be achieved, either by using long polymerisation times (i.e. the length of time in which a specified amount of catalyst for polymerization is used what either

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the duration of the bulk polymerization or the average residence time in the polymerization reactor ⁼ "- means in the case of continuous polymerization) or by using somewhat shorter polymerization times and working under higher than usual pressures and / or in some cases under higher than usual temperatures the method according to the invention is preferably reduced

* wisely performed on prints that are higher than those for the previously known Ziegler processes. For example, in the case of ethylene polymerization

the present invention at pressures above 8.033kg / cm (100) and preferably on the order of (200) 15.33 to (1500) 106.33 or greater e.g. B. at about (500) 36.033 to (1000 psi gauge) 71.033 kg / cm ² , although the pressure used will of course depend on the type of polymerization equipment. The present invention can with

"be carried out with particular advantage, for example in the case of ethylene polymerization and copolymerization at pressures above (500 psi gauge) 36.033 kg / cm. The rate of polymerization is also temperature dependent, but generally can be the upper temperature limit in the case of polymerization be determined according to the invention by the need to work under conditions that results in a suspension of a solid polyolefin product in the liquid phase of the reaction mixture,

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ie a slurry mentioned above, although it is not essential that the immediate polymerisation product be a slurry as it is possible to make a polyolefin solution from which the solid polyolefin is precipitated, ζ. As by cooling prior to its recovery "Preferably, a polymerization according to the invention at a temperature between 60 and IQO ⁰ C and at a pressure which is higher than 36.033 kg / cm (500 psi gauge), performed *.

When carrying out the olefin polymerization according to the invention, the olefin to be polymerized or the olefin mixture can be added to the reactor in gaseous or liquid form and the liquid phase of the reaction mixture can be a solvent and diluent and / or the liquid olefin monomer, depending on those used. Conditions and the type of olefin to be polymerized. Is a gaseous olefin addition performed _v as the feed may optionally have an inert ingredient or ingredients such as saturated hydrocarbons and / or hydrogen as a molecular weight at appropriate concentrations, as is known. Hydrogen or some other molecular weight may also be used when the reaction mixture contains a liquid olefin. Bit molecular weight modifier is usually necessary * as laohmana is aware of a polymer

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manufacture product with suitable processing properties. According to the invention, a polymerization time is selected that is the same under the conditions used gives a desired yield of polyolefin product per unit weight of transition metal in the catalyst ", which is contained in the reaction medium. In general, such a yield will be at least 10,000 g of polyolefin per g of transition metal. While

"During this polymerisation time, the concentration of the organometallic component of the catalyst will generally fall as a result of side reactions with trace impurities in the reaction mixture and / or the effectiveness of the Ziegler catalyst may decrease as a result of the decrease in activity over time like it occurs in some organometallic catalyst components £> ie SiLymerisation but can be maintained at the desired speed by operating under substantially gleichmäßigeil conditions, including continuous or growing (incremental) addition of the catalyst to the reaction mixture to> ^r the desired concentration in to maintain the reaction mixture, along with the continuous

ι -

[Growing or removal of the polyolefin reaction _a mixture to obtain the polyol-finproduktes thereof, or with a fresh batch polymerization by the addition of organometallic compound to the Reaktioßsmischung.

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The present invention can be carried out for polymerization and interpolymerization each

OC -olefines- produced with the help of a Ziegler catalyst of the type mentioned above is polymerizable, and the olefin can be either liquid or gas under the conditions used be »although it is special for the polymerization of ethylene and propylene and the copolymerization of ethylene with propylene or butene-1 is applicable, e.g. B. in smaller quantities up to about 15 wt .- ^ ethylene * Generally can the polymerization, apart from the special conditions mentioned above, in that for Ziegler polymerization known manner, and with the usual precautions such as the purity of the reactants and, where appropriate, the inert liquid solvent or the diluent component of the reaction mixture and the exclusion of air and water. Polymerization modifiers can optionally be used are present and the polymerization can be carried out continuously or batchwise. In case of continuous polymerization in a polymerization zone containing the reaction mixture to give the olefin monomer, liquid diluents or solvents if used and fresh catalyst continuously is added and from which the polymer product, liquid Thinner or solvent, if present, and catalyst is continuously removed around the Polymerization in the zone or essentially at the same time.

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To carry out moderate conditions (which includes maintaining the above-mentioned maximum concentration of metals of Group 4A, 5A or Sk ), the average residence time of the reaction mixture in the polymerization zone is preferably such that the weight of the polymer formed is at least 10,000 times the weight of the group 4A, 5A or 6A metal removed from 'the polymerisation zone' together with the polymer product.

The immediate polymerisation product will normally be a slurry (i.e. a suspension) of solid polyolefin in a liquid phase containing liquid polyolefin and / or an inert liquid diluent or solvent (e.g. isooctane, pentane or a petroleum distillate in the boiling range 100 to 120 ⁰ O) containing in the dispersion, ie both in solution and also in suspension, the catalyst and / or the ψ decomposition product or derivative of the catalyst.

A certain quantity of catalyst and / or its decomposition product or its derivative, is usually associated with the polyolefin in some Heise. .Kr- * according to the invention, the immediate polymerization product can be subjected to a simple physical treatment to obtain the solid olefin, e.g. B. by separating the polyolefin from the liquid phase by filtration, centrifugation or evaporation. No chemical treatment of the polymerisation product or the obtained one

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Polyolefin is necessary or used in the practice of the invention and the polyolefin obtained can simply be dried in any known manner, e.g. B, by steam treatment in one. Ejector or followed by jet distillator if necessary is through fluidized bed drying »whereby the polyolefin comes into contact with warm nitrogen or air about the moisture and the last traces of liquid Remove thinners and solvents. The dry one Polyolefin is then either processed directly into molded parts or in particulate form around this the Plastics industry for the production of molded parts to deliver. Bs it is clear that the present invention not the addition, for example to the dried polymer, before or during processing, of polyolefin additives for example antioxidants, light stabilizers, casting additives, antistatic agents and pigments or Dyes as it is necessary in polyolefin products, excludes. Optionally, the reaction mixture, in which the polymerization is carried out, too Additives to be incorporated into the final polymer product provided, of course, that such Additives do not affect the polymerisation. Examples such additives are finely divided fillers that can also act as a catalyst carrier under certain circumstances. ,

The present invention is illustrated by the following examples explained, whereby the ratio of parts by weight to parts by volume is as it prevails between kg and 1 *

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example 1

A polymerization reaction medium containing a Ziegler catalyst dispersion is prepared by adding sufficiently preformed p IiOl ^ to a solution of aluminum trialkyl in a petroleum distillate (boiling range 90 to 120 ⁰ G at normal pressure) to form a dispersion which is 0.05 mmol per liter of titanium and 1 mmole per liter of aluminum. The 9 -TiOl is made by reducing

with aluminum triethyl followed by heating at 160 ⁰ G. The aluminum trialkyl used to form the catalyst dispersion is a mixture of long-chain trialkyls with alkyl groups, each containing 14 to 14 carbon atoms, which were formed from the reaction of aluminum triisobutyl with a mixture of Ο .., to O-to'Ol-olefins under the conditions of the alkyl group shift.

A Polymsrisationsreaktor with 1500 parts by volume derKatalysatordispersion is charged with an ethylene / Wasserstoffmisdhiung with equal volumes of ethylene and hydrogen and the polymerization is conducted at 9O ⁰ C under a pressure (in the G-asraum above the liquid) of 15.033 kg / cm ² (200 psi gauge ) performed for 20 hours. After this polymerization, the olefin product is separated from the reactor slurry by filtration and the filter cake is then jet distilled and dried. A total of 126 parts by weight of polyolefin will be

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obtain. This corresponds to a yield of 17,900 g Polyolefin per g TiClr ,. .

In a further polymerization of ethylene by means of a Z ^ gler catalyst dispersion in Cyelohexan at 9O ⁰ C wird.die polymerization at (1000 psi gauge) 71.033 kg / cm carried out and it is possible in this way a high yield of polyethylene according to a polymerization can be achieved in just 1 hour. In carrying out this further polymerization of the catalyst dispersion containing reactor at 9O ⁰ C with purified hydrogen at a pressure

2
of 36.033 kg / cm (500 psi gauge) and thereafter with

ο
Ethylene was injected to 71.033 kg / cm (1000 psi gauge), the pressure being maintained during the polymerization by adding ethylene if necessary.

In both cases the polyethylene produced is for Can be processed into molded objects without further chemical cleaning. Such objects could be direct or more conveniently first preformed by forming small particles (chips) and using this for the production of molded articles.

Example 2

An autoclave is cleaned thoroughly and then with pure nitrogen purged to remove traces of oxygen and

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remove adsorbed barrel. Sr will & am aalt

visit Lokt »the ä $ if 6® ° Ö in; 3 ^{ 0 MIn- heated« ir-de u

and Durehfolniibb «rn of
asstgk'eil; * A lot
tem feöiiesfl% Glotee> an ig Given to -ei. »«

From 1.2 mmol per 3Jit «ir -

the local teae! solution -will be datifi on BO ⁰ O Ιΰ 5Ώ Miss.

^ heated. line amount preformed to the ai ^ calibrated to give a iConzentration of Q »018 per 1, then & u of the hot solution was added (as a suspension in 2" Vol. "parts" liquid hydrocarbon) and the obtained mixture to 90 ⁰ G heated.

The autoclave is then set to 36 * 033 kg / cm (500 psi gauge) brought to a final pressure of 71.033 kg / cm (1000 psi gauge) with hydrogen and then with purified ethylene. F Under these conditions the polymerization begins and is continued by adding ethylene with a rate sufficient to maintain a pressure at 71.033 kg / cm (1000 psi gauge) in the autoclave • to hold * After 60 minutes, the autoclave is vented and the contents are cooled to ambient temperature. The polymerization product is filtered and the solid polymer is oven-dried, with a yield of polyethylene a melt index of 0.07, which is 12,500 g KLyäthylen per g titanium trichloride.

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The obtained polyethylene is with a usual phenolic antioxidant mixed and then by extrusion of a heat-plasticized polyethylene mass processed into threads * which are then cut into snippets will. These scraps are used to manufacture molded articles by injection molding.

Example 3

According to the invention, polyethylene is prepared by polymerizing ethylene in the presence of hydrogen (the gas space in the reactor contains equal volumes of ethylene and hydrogen) in the general manner described in Example 1. Polyethylene is prepared in accordance with the invention. Various titanium catalysts and catalyst concentrations are used as shown in the table below, which also relate to the other conditions used and results obtained. In [each case, the polymerization is carried out in a reaction mixture containing a liquid diluent (hydrocarbon) from which the polyethylene product is physically separated before it is extruded into shreds (i.e. without chemical cleaning) for testing purposes. The melt index of polyethylene products - is determined according to the ASTM melt index methods. The ß and ^ forms of titanium triochloride are produced by reducing titanium tetrachloride with aluminum triethyl followed by heating at 160 ⁰ O in the case of the t ^ form. ~

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Polym. pressure
Temp.

G (psi) atü

Catalyst ■, (mmol / 1 in React.Gem)

Titanium component organometallic

Component Polymerization Yield Melting Time ■ Polymer Index des

(g / g polymers; titanium g / 10 min h component)

90

(900) 63

0.04 -TiCl,

3.0 χ AlAtοCl 10,000 0.33

(looo) 70 0.03

-TiCl,

(100O) 70 0.025

-TiCl,

(1000) 70 0.03

-TiCl,

5, P

AlAt ₂ Cl

5.0

AlAt ₂ (OAt;

5.0 AlIt ₂ Cl 10.600 0.31

12,600 0.26.

10,500 0.34

90

90

(1000) 70 0.03

ii

(1000) 70 0.03 ß-TiCL

5.0 AlAt ₀ Cl

5.9 AlIt ₂ (OAt) 1.5

1.5

13,000

12,500

0.68 0.86

3 =; Aluminum diethyl chloride

xx = aluminum diethyl ethoxide

The polyethylenes obtained are suitable for processing into pesticide particles, which are suitable for the plastics industry for molding moldings, whereby a phosphate dioxide is added to the polyethylene prior to processing.

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Example 4

wiri erf i ^ diuMgsgeaa & ß natef ^ erwe & duag ■ one

polymei-isiejft »The ^ polymerisation ■ is ß ^ chgefühifc, i« r ^ gesfiwart ir-on IO ^ .W ktfa $ l®n} im © iuier fl .sisLgsii, the 0.02 ^

Bas f ^s er £ aüa ^ em indicates the Ziagalae tea? desired (as metalloirganisoihe

of the catalyst) zxk the reaction mixing at € 5 -C

which is pressed down to 71.033 kg / cm (1000 ρ si "gauge)

vi.orde: n is _{; f} first dui-cia addition of vm ". hydrogen, which increased the 'pressure to 15.033 kg / fcm ^ (2OC psi gauge),

f.efOlgt of ethylene, which increases the pressure on the value of .71.033 kg / cm (10000 psi gauge). After 30 kin, meanwhile the reaction mixture is agitated at 65.degree

became the required amount of vanadium components 3ek. Butyl vanadate, added and the Polym

then started. The 'polymerization was continued at 65 ° 0, with the pressure at 71.033 kg / cm (1000 psi gauge) by adding ethylene if necessary.

There were 2 polymerization attempts under different Conditions as indicated in the table below, carried out (which also contains the results obtained) and the polymer product was through physical

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Separation from the liquid phase of the reaction mixture as described in Example 1 obtained. The Rührgesehwind igke it was 1,100 rpm.

Catalyst components Polymerization polymer melt concentration time yield index of the mmol / 1 polymer React. H - g / g V g / l0 min

4, OAlIt ₃ + 2.25 l, 65xlO ⁶ 0.69

0.002 see -.

Butyl vanadate

4.0 AlAt + 1.0 L, 3xlO ⁶ 0.8

0.0Ό4 sec - "

Butyl vanadate

In this table the abbreviation means aluminum triethyl.

The polyethylene thus obtained was processed into solid particles by extrusion molding; the particles obtained are suitable for shaping into objects. . ■

Example 5 .

Polyethylene, with a Schiaelzindex of 2.0, according to the invention is continuously produced in a stirred autoclave ^1, the half-filled with a liquid

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.Reaction mixture is driven, which contains a dispersion of a Ziegler catalyst based on lithium in a hydrocarbon diluent. The catalyst contains beta-titanium trichloride and aluminum triethyl and the concentration "amounts to 0.03 and 2.0 mmol per liter Reajfctionsmischung. The polymerization temperature and, the pressure is 80 ⁰ C and 1000 psi (gauge) 71.033 kg / cm During the polymerization, the Continuous polymerization mixture, discharged from the autoclave to separate the polyethylene at a rate such that the average residence time in the autoclave is 5 hours; fresh hydrocarbon diluent and catalyst are continuously added to maintain a constant volume of a reaction mixture and catalyst concentration. The autoclave is opened at the beginning with ethylene and hydrogen in a ratio that the gas space in the autoclave above the liquid reaction mixture has 47 vol .- $ ethylene and 53 vol .- $ hydrogen. During the polymerization, ethylene is continuously added to the autoclave, together with a small amount of Hydrogen, in order to keep the main composition of the gas phase in this volume ratio *

The polyethylene product physically obtained from the reaction mixture from the autoclave in the process described in Example 1 Way, is obtained in a yield

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which corresponds to approximately 25,000 g of polyethylene per g of TiCl. Bs is extruded into fibers that are cut into particles. These particles are for molding suitable of objects.

Claims

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Claims (12)

j "1 .. ^/ Process for the production of a polyolefin product ^ - in the form of objects or solid particles, which are suitable as starting material without prior purification for the production of molded bodies in the plastics industry, thereby geke η η ζ eich η et that one is an olefin or polymerized an olefin mixture in a reaction mixture which contains a dispersion in a liquid phase of a Ziegler catalyst which contains a mixture of a) a compound of a metal of group 4A, 5A or 6A of the periodic table, in which the metal of the compound in a valence state which is lower than the normal valence of the metal, and b) an organometallic compound of a metal of Group IA, 2B or 3B of the periodic system, and polymerization conditions which maintain a concentration of the metal compound of Group 4A, 5A or 6A in the reaction mixture, which is so large that the concentration of the chemically bonded metal of group 4A, 5A or 6A is below C, 15 mmol of metal per liter of liquid phase of the reaction mixture, and the solid polyolefin is obtained from the reaction mixture and used for the production of molded bodies or solid particles in a heat-plasticized state without prior chemical cleaning holds. ■ - ■ _ ₂ _ 0 0 9 8 20/169 * BATH 28 LA-30 015 2. The method according to claim 1, characterized in that the concentration of the metal , Group 4A, 5A or 6A compound sets so that the concentration of the chemically bound metal of group 4A »5A or 6A below 0.1 mmol metal / l liquid holds. 3. The method according to claim 2, characterized in that g e k e η η - w draws that a metal from group 5A is used and the concentration of the chemically bound
Metal between 0.0005 and 0.01 mmol metal / l
Holds liquid. · 4. The method according to claim 3, characterized * gek β η η ζ eich η et that one is a metal compound
which contains vanadium as the group 5A metal. . 5. The method according to claim 2, characterized in that geke η η is a metal bond of the
Group 4A is used and the group 4A chemically bound metal concentration is maintained between 0.01 and 0.1 mmol metal / l liquid. 6. The method according to claim 5, characterized in that titanium is used as the metal of the group
4A used. 0 0 9 8 2 0/1691 lA-30 7. The method according to claim 6, characterized in that the concentration of the chemically bound titanium between 0.02 and 0.08 mmol titanium / 1 ί holds liquid, 8 »Method according to one of claims 1 to 7» thereby g e k e η η ze i c h η e t that one is an organometallic Component of the catalyst used that does not contain halogen in the molecular structure. 9. The method according to any one of claims 1 to 8, characterized g e k e η η ze i c h η e t -j- that the polymerizatian at a pressure in excess of 36.033 kg / cm (500 psi gauge). ' 10. The method according to any one of claims 1 to 9 »characterized in that the polymerization is carried out continuously under substantially uniform conditions and with an average residence time of the reaction mixture in the polymerization zone which is so large that the polymer weight is at least 10 000_fold Weight of the metal of group · 4A, bA or 6k , which is removed from the zone together with the polymer ]. 11. The method according to any one of claims 1 to 10, characterized characterized that one is the immediate _4_ 0 0 98 207 169 1 LA-30 015 or final polymerization product as a slurry of the solid polymer in a liquid medium, from which the polymer product is physically separated before the latter becomes a molded body or a Solid particles is processed. 12. The method according to any one of claims 1 to 11, characterized characterized in that the olefin is ethylene polymerized, ° 62X11 009820/1691