DE2233983A1 - IMPROVED HIGH DENSITY ETHYLENE POLYMER BLEND AND POLYMERIZATION PROCESS FOR THEIR PRODUCTION - Google Patents

Description

H Ε / Κβ (465) 15,533-F

Improved High Density Lithium Polymer Blends rr: .d Polymerization Processes for Their Manufacture

Priority: U.S.A. July 13, 1971 by Ser. No. 162.313

The invention relates to ethylene polymer mixtures of high levels Density. It relates to particular ethylene polymer mixtures. of high density with improved impact strength and improved stress corrosion resistance. She concerns also a Ziegler polymerization process for the preparation of these mixtures. '.

The subject of the invention is, on the one hand, a homogeneous ethylene polymer mixture which is solid under normal conditions and which consists of a predominant amount of an ethylene polymer of high density and medium molecular weight and a smaller, but not less than 3% by weight, amount of a high molecular weight, non-elastomeric Ethylene and 'an alpha-olefin produced copoly ^ iaren with a crystallinity of at least 5% and eiiic ^. Content of alpha-olefin comonomer of 2 to 40 wt.% Of the copolymer, wherein the polymer determines the Schmelzflußviskosität medium molecular weight, according to ASTM D-1238-65T (E) is at least Jünfmal so.hoch as the high molecular weight ethylene copolymers and Schmelzflußviskosität of the amount of the alpha-olefin comonomer contained in the medium molecular weight ethylene polymer is in the range between zero and one third of the amount of the alpha-olefin comonomer contained in the high molecular weight copolymer.

The invention then relates to a process for the production of ethylene polymer mixtures of high density,

209 884/1262 '

that consists in that one (l) ethylene or a mixture from ethylene and an alpha-olefin comonomer in one Solvent, and in the presence of a Ziegler catalyst at solution polymerization temperature in a main zone polymerized under such a pressure that essentially no vapor phase is formed and that all reactants remain in solution under conditions under which an intermediate molecular weight polymer is obtained will; that one (2) ethylene and another alpha-olefin or other alpha-olefins in such a ratio polymerized in a sub-zone in the presence of a Ziegler catalyst and under the conditions of a low-pressure solution polymerization, that a high molecular weight, non-elastomeric copolymer is formed which has a crystallinity of at least 5 / S and of one predominant amount of the ethylene polymerize and out at least 5% by weight of the polymerize other alpha-olefin and that (3) the products obtained in the two polymerization zones are in the liquid state in such a denomination that a Ethylene polymer mixture of high density is formed, which contains the polymer of the main zone in predominant amount.

It has been shown in practice that the ethylene poly- ' .Merene mixtures according to the invention are homogeneous and lighter can be processed as polymers with a narrow molecular weight distribution. Surprisingly, are the '-homogeneous mixtures according to the invention in their stress corrosion resistance and their impact strength are those of the high density obtained in the one-stage polymerization .Ethylene homopolymers and ethylene copolymers and mixtures of these ethylene homopolymers and ethylene copolymers with ethylene homopolymers and / or ethylene copolymers other than those used according to the invention and described above Clearly superior to high molecular weight copolymers made from ethylene and an alpha-olefin.

209884/1262 '' ^^

BATH ORIGINAL

2233S & 3

The mixtures according to the invention do not have one alone improved stress corrosion resistance and impact strength, "sondera, for example, are reduced by their Schnielz viscosity at high shear stress. excellent processable, you 'are suitable for the manufactures! - treatment of cable jackets, bottles, and other containers such as bowls, vats, cans, pails, and barrels ^ as well as, of films, foils ,. Threads and a lot of changes, molded objects. . / "

The ethylene polymer mixtures according to the invention of high density contain, in a preferred composition, at least 60 % by weight of the ethylene polymer with an average molecular weight and 5 to 40% by weight of the high molecular weight niciitelastomeric copolymer of ethylene and an alpha-olefin. Bevorzugt.hat the mixture at this relate »eiiieii total content of 0.06 to 24 wt.% Äri polymerisi'ertem alphaE-Oiefihcomoilomeren, a SchmelzflüÖviskösität from 0.1 to 30 dg / mih. and a density of at least 0.930 g / cm. Particularly preferred are mixtures with a comomer content of 0.5 to 15 wt. g / cm. On öieisten is preferred Gemis.che having a density of east; 946 to east, ⁱ 9S4 g / CiÄ>, a SchmelzflUßviskbsität of 1 ^ 0 to 10jO dg / Miki iäiid an IZOD impact strength of 0 ^ 7 biö 1OjO barren raw ·.

The expression "ethylene polymer with average molecular weight" denotes a homopolymer of ethylene! J a co-polymer of ethylene and an ipha oil with a predominant content äh polymerised ethylene and a lower content, for example a GeEaIt. of up to 13 Gew. ^ ^r , in a pöiymerisierteii älph'ä ^ Öie ^ "f. in or more such alpha-olefins - _t and GemiSeh% ·" of the two. The ethylene polymer of medium molecular weight contains, based on them by weight; vöi * zugsweiäS

0 to 6 weight percent polymerized alpha olefins. A polymer of this type preferably has a density of 0.945 to 0.970 g / cm and a melt flow viscosity of 0.5 to 500 dg / min. A polymer with a density of 0.955 to 0.970 g / cm and a melt flow viscosity of 1 to 400 dg / min is particularly advantageous.

The term "high molecular weight, non-elastomeric copolymer of ethylene and an alpha-olefin" denotes a thermoplastic copolymer of ethylene and an alpha-olefin or several alpha-olefins and mixtures of these copolymers which have a crystallinity of at least 55p. The copolymer has, based on its weight, a total content of alpha-olefin monomers of at least 2% by weight. In a preferred composition of the copolymer, based on its weight containing a total of 2 to 40 wt,%, advantageously 3 to 20 wt.% Alpha-s-Olefineomonomeres and at least 60 Gew.?o, advantageously 80 to 97 wt.% Ethylene. It preferably has a melt flow viscosity from 0.0001 to 6 dg / min., More advantageously from 0.003 to 1 dg / min., A density from 0.870 to 0.955 g / cm, more advantageously from 0.880 to 0.945 g / cm and at normal room temperature Crystallinity of at least 5%, preferably of at least 10%. Most advantageous is a crystallinity of 10 to

In the case of the aforementioned polymers "and copolymers," alpha-olefin ¹¹ denotes an aliphatic alpha-mono oil fin with 3 to 12 carbon atoms. Examples are propylene, butene-1, pentene-1, hexene-1, heptene-l _f octene-1, nonene-1, dodecene-1 and mixtures of these alpha-olefins mentioned. Preference is given to using 1-butene and, in particular, propylene.

It is essential for the invention that the content of the high molecular weight copolymers of alpha'-olefin monomers

20988471262

at least three times, "preferably at least ten times as large is like that of the medium molecular weight ethylene polymer. It is also essential to the invention that the melt flow viscosity of the polymer with an average molecular weight at least five times) "preferably at least ten times as large is like that of the high molecular weight copolymer. It is for the purpose of. Invention advantageous if the '"equivalent density" of the high molecular weight copolymer by at least 0.01 g / cm lower is than the density of the medium molecular weight polymer. . '"' ·"

By "equivalent density" is meant the density that the high molecular weight copolymer would have if it had the same melt flow viscosity as the medium molecular weight ethylene polymer. If the melt flow viscosity of the polyethylene decreases by a factor of 10, the density decreases by 0.004 g / cm. ^{For example, a polyethylene with a density of 0.966 g / cm "5} at a melt flow viscosity of 10 dg / min, an equivalent density of 0.950 g / cm" 5 at a melt flow viscosity of 0.001 dg / min.

The crystalline proportion or the degree of crystallization of the high molecular weight copolymer is expressed by the percentage by weight that the crystalline material has in the total polymer. The degree of crystallization of the copolymer is determined using a differential calorimeter in which the temperature of a test strip of the copolymer is increased by 10 ° C. per minute by the addition of heat and the heat flow is recorded. If, you can melt that! The amount of heat required for the sample is calculated: the degree of crystallization of the copolymer is determined by comparing the amount of heat calculated for the copolymer sample with the amount of heat required to melt a corresponding sample of a polyethylene with a degree of crystallization of 10 yu.

209884/12 62

The process according to the invention can be used both continuously as well as discontinuously. In practice, "one prefers a kop.ci.-iui ^ rlio" "=". Way of working. Furthermore, the process steps I and II can be divided into two ' as the main polymerization zone .bzw. as the secondary polymerization zone used reactors either simultaneously, i.e. in parallel with one another, or one after the other in the manner of a staged process carry out. In the latter case, the polymerization is carried out in one of the two reactors under certain conditions, the polymer formed in this way then passes into the with further monomers charged second reactor over and leads in this the polymerization is carried out in the presence of the polymer fed in from the first reactor and kept in the dissolved state under changed conditions. The two reactors can be used in any sequence.

In the preparation of the ethylene polymer of medium molecular weight, the monomer stream consisting of ethylene or a mixture of ethylene and an alpha-olefin is introduced into the main polymerization zone charged with the dispersion of a Ziegler catalyst in an inert liquid diluent. The polymerization is performed at Lösungspolymerisationstemperatur under a relatively low pressure, for example under between 20 and 40 atm depending on the solvent and on the temperature ·., Fluctuating pressure, and preferably in the presence of a molecular weight controlling agent, for example hydrogen, by. ΚζΛ uses "the hydrogen, based on the total amount of monoborane, in a concentration of 0.1 to 5 mol / o, most advantageously in a concentration of 0.3 to 2 vol. Vol., Preferred after the polymerization in the main zone The procedure used is to introduce the hydrogen as part of the Konomorenntroms into the main zone.

2 0 9 8 8 4/1282

BATH ORIGINAL

22339Β3

ratio in the catalyst by adding monomers and! Please dis- the regulation of the monomers ■ used reaction temperature, as well as by other means as l / ate substance, for example with 2,3-dichloropropene-1, Styrene and other unsaturated hydrocarbons ^ ■ substances as alpha-olefins, for example acetylene or Control combinations of such hydrocarbons. The monomer mixture introduced into the main zone consists of ■ 70 to 100 mol / 50 ethylene and 0 to 30 mol of the alpha-olefin comonomer, preferably from 85 to 100 mol $ o ethylene and

0 to 15 Mo 1% alpha-olefin.

In the production of the high molecular weight copolymer from Ethylene and an alpha-olefin are preferred • from 60 to 90 MoI ^ q ethylene and 10 to 40 MoISo of an alpha-olefin into the existing monomer stream into the one with the dispersion of a Ziegler catalyst in a pied liquid Diluent feeds a minor polymerization zone; a. The polymerization is carried out at the solution polymerization temperature under a relatively low pressure, for example under a depending on the front Solvent and the temperature between 20 μι-id 40 atm. fluctuating pressure. To give the polymer produced in this zone the highest possible molecular weight it is advisable not to give any to use the molecular weight controlling agent or such an agent only in a small amount, e.g. in the case of hydrogen, based on the monomer mixture,

1 MoI ^ should not be exceeded. One prefers to work but in the absence of such a control means

and among those, the temperature and. Conditions relating to the catalyst such that the melt flow viscosity of the copolymer obtained is only up to one fifth as high as the melt flow viscosity of the polymer having an average molecular weight.

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BATH ORIGINAL

The reactors used in both polymerisation zones preferably stirred tanks that allow the moderate pressure applied endure. I-Ian can also use tubular reactors, yet 'nut these with a multitude of task openings be provided so in the manufacture of the high molecular weight Copolymers ensures the copolymerization of the alpha-olein is.

The known Ziegler- · Catalysts. These catalysts are known to be mixtures of compounds of the metals of groups 4b, 5b, 6b and 8 of the Periodic Table ("Handbook of Chemistry and Physics" of the Chemical Rubber Company, 48th edition) or of manganese with organic metal compounds of an alkali metal, an alkaline earth metal, zinc, a 'Earth metal' or a rare earth metal. The ZJegler catalyst used for the purposes of "the invention is preferably the reaction product of a reducing organometallic component in which the metal is aluminum, and a reducible compound of a transition metal in which the transition rivet is titanium.

As examples, organometallic compounds preferably used bonds are the aluminum trialkyls, for example Aluminum triethyl, aluminum tripropyl, aluminum triisobutyl and other aluminum trialkyls in which the alkyl contains 1 to 12 carbon atoms, dialkyl aluminum halides, for example dietary aluminum chloride, diisobutyl aluminum chloride and other dialkyl aluminum halides in which the alkyl contains I to 12 carbon atoms and the halide is preferably a chloride, but • can also be a bromide, an iodide or a fluoride, as well as alkyl aluminum hydride and alkyl aluminum alkoxide called.

A halide, an oxyhalide, is preferably used as the reducible compound of a transition metal

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- C _

Alkoxide, a cyelopentadivinyl or an acetylacetonate \ of reducible titanium. Reducible titanium means nan titanium - that in the tetravalent and trivalent state occurs. Titanium tetra- .. is used with particular preference.

Chloride and titanium trichloride in the beta, alpha or gamma-crystalline form and the analogous compounds of vanadium and zircon;

For the polymerization of the monomer or monomer mixture The Ziegler catalyst is used in the manufacture of the medium molecular weight ethylene polymer with particular preference a mixture of titanium tetra-chloride and aluminum triethyl or aluminum triisobutyl, a mixture of titanium trichloride, especially that of the beta form, and aluminum triethyl or aluminum triisobutyl, ■ a mixture of titanium tetrachloride and diethyl aluminum chloride, a mixture of titanium trichloride and diethyl aluminum chloride or a mixture of titanium trichloride and ethyl aluminum trichloride or isobutyl aluminum dichloride .. "... -

It is used both in the main polymerization zone or first zone and in the secondary polymerization zone or second zone of the said catalysts those in . which the reducing organometallic component and the reducible transition metal in one. Molar ratio from 0.3: 1 to 40: 1, preferably from 0.5: 1 to 20: 1.

The catalyst to be used in both zones is preferably prepared in such a way that the reactants corresponding to its composition are first mixed before it is introduced into one or the other of the polymerization zones. However, it can also expediently be produced by introducing its reducible metal-organic component and the reducing transition metal directly into the zone at the same point or at different points ^. The catalysts used in the two cells can also be different from one another.

209884/1262

- OK -

".'isnn the polymerization of the Γ-Ιοηο-ΐηοΓΘΐι or of the ϊ-ίοηο-merengemix.es in the two polymerization zones. carries out each other, the polymerization in one zone being followed by the polymerization in the other "Zone follows, then, unlike in SchlaiTinipoly-rnerization, in solution polymerization, because of the short life of the catalyst, little or no active activity Catalyst from the first to the second zone, even if the entire reaction mixture is transferred. Even though in a process operating in stages, fresh catalyst is added in such an excess in the first zone If active catalyst can get into the second zone, it is more expedient to have fresh catalyst in each of the two zones to add. If, on the other hand, the polymerizations carried out parallel to one another in both zones, fresh catalyst must be added to each of the two zones. Under Fresh catalyst is understood to be a catalyst whose particles do not have any polymer chains or chains that are when working in two stages in the first stage of polymerization form, adhere.

The concentration of the catalyst is a means of controlling the conversion of the monomer to the polymer and to some extent also to control the molecular weight of the polymer produced in the two zones. The catalyst is in each of the two zones in a catalytic). Amount available. As a general rule, that the concentration of the catalyst, on the transition

-5 -3 related to metal as a component, between 3x10 and 1.5x10

-5 -3 millimoles per liter, preferably between 8x10 and 1x10

Millimoles / liter can fluctuate.

That as a carrier for the catalyst and for diluting the The diluent used in the reaction mixture is liquid under the reaction conditions and essentially inert.

209884/1282

BAD ORlGtNAt

Preference is given to using as a diluent. Mixtures of saturated hydrocarbons which boil ^{between 60 and 200 ° C.} ':

Although for the ■ method according to the invention technical Ethylene and technical olefin monomers and diluents with the usually own degree of purification can use, one gives-purified monomers and diluents, i.e., those that are relatively free of impurities, are decidedly preferred.

It is useful to start the polymerization in the two zones to carry out under conditions under which the solubility of the polymer in the inert liquid dilution-snijTct'el preserved. Bs is also useful in each polymerization zone and beyond that throughout. System to prevent an excessive pressure drop like him for example with highly viscous solutions, and on the other hand to get rid of problems that arise, when the polymer is used when very large amounts of diluent are used to be recovered nut. With this in mind, it is advisable to adjust the amount of diluent to be dimensioned so that the concentration of the polymer in the solution leaving the two zones is below 20% by weight, preferably between 5 and 15% by weight. In In practice, the diluent is used either with the catalyst stream or the monomer stream, or with both Flock to. Kan can into the two reaction vessels introduce further diluent if required.

The term “solution polymerization temperature”, when applied to the first and second zones, denotes a temperature which is at least above the precipitation point of the polymer formed. This temperature is generally in the range irn from 120 to 220 ⁰ C ,, more specifically in the range 135-180 ⁰ C. Preferably the reaction is carried out at a temperature of about 150 ⁰ C.

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mmimn ^ '© ad original

■ 2233883

The one in the first and the second. Polymerization Zone Applied pressure is not particularly relevant to the invention. You work with. Advantage under one Pressure from 20 to 40 atm., Preferably at a pressure of 35 atm »« However, depending on the solvent and the polymerization temperature, pressures of 10 atm. and those of 50 atm. and more can be applied *

Maii carries out the polymerization after one for the low-pressure polymerization of alpha-monoolefins according to Ziegler characteristic processes.

The polymerization time is not an essential feature of the invention. One can choose the polymerization conditions so choose and "coordinate" that the polymerization time in the first zone or in the second zone vary between a few minutes and several hours can;

In continuous work according to the parallel process, it is preferred that fresh monomer * the diluent and the catalyst, continuously into a first or a second polymerization zone with a running stirrer, each zone running the Removes the reaction mixture formed in it and the two ■ Mixes together in the liquid state immediately after they have been removed from the two zones. Under "liquid Condition "is understood to mean that the polymer is either in Lo'suiig or that it is held at a temperature at which solidification does not occur.

A continuous operation according to the step process consists in a preferred manner that fresh monomer ■ meres, the diluent and the catalyst in one
of the two polymerization zones with the stirrer running
givesj the reaction product formed from this in the
second polymerization zone and into this.

209884/1262

at the same time fresh I-ionomer, diluent and Catalyst initiates continuously.

The speed of the agitators in both zones is'G both in the parallel procedure and in the step procedure not essential to the invention. It is expedient to use running speeds such as those used in low-pressure, Polymerization according to Ziegler are common, which are therefore sufficient for a uniform distribution of the reactants in the reaction mixture.

The polymer mixture according to the invention is recovered balca.nnte way from the liquid diluent, for example by removing the solvent after the catalyst has been deactivated. You can do this isolate the polymer mixture first from the combined reaction mixtures and then remove catalyst residues therefrom remove known way. According to a preferred execution; Approximate form, however, the catalyst residues are removed directly from the combination containing the polymer mixture the reaction mixture and treated this with an alcohol. for example methanol, ethanol or Isopropanol, an acidified alcohol, or a similar polar liquid. You can also use several means use one after the other, for example an Aiko hol and hydrogen chloride .. '

The following examples are intended to explain the invention in more detail without restricting its scope. In the description and in the examples, the expression "melt flow ^{viscosity 11} , determined in accordance with ASTM D-1238-65T (3), denotes the flow properties of the polymers, expressed in decigrams (dg) per minute, and the expression" density "in accordance with ASTM D- 1505-63T determines the absolute density of the polymers, expressed in grams per cubic centimeter. In the examples, unless otherwise stated, parts and percentages are parts and percentages by weight.

209,884 / 1.2 ^{6: 2; '':?}

- Ik - .

The catalyst dispersion used in the examples and its preparation, the reactors also used and the method of operation are described below:

1. To prepare the catalyst dispersion, mix in the sequence of their listing

39.9 kg dry isooctane with 8.2 "■ titanium trachloride and 26.3 "a 15% aluminum triethyl solution

in isooctane

under nitrogen at a maximum temperature of 38 to 50 ° C. The aluminum triethyl and the titanium tetrachloride have a molar ratio of about 0.8: 1.

2. Is used in the main zone or first zone one Steam-heated insulated one equipped with a stirrer Reactor of spherical shape with a capacity of 946 1 and in the sub-zone or second zone Also equipped with a stirrer, steam-heated insulated reactor of spherical shape with a capacity of 83.3 1.

3. As described, the two reactors are operated continuously Working method either, in a parallel process at the same time or in a step process one after the other used. In operation, they are flushed with nitrogen, charged with isooctane and placed on a certain Temperature heated. To the same extent as he with - the reactances is charged, the reaction mixture is removed from the reactor used as the first zone.

example 1

In this example, the reactor will be the secondary polymerization zone and the reactor of the main polymerizations ::, onein used simultaneously in a parallel process. One passes into the charged with isooctane and at 150 ° C and

209884/1262

P-uiiter one. Pressure of 32.5 kg / era 'held secondary reactor an hour from 9.5 - leg ethylene. 10 kg of propylene and 185 kg of iso-octane of an existing carbonaceous mixture are continuously borrowed and at the same time continuously adds about 0.14 kg of the catalyst dispersion per hour. The. The reaction is kept at a temperature and pressure of 5 kg / cn. Since it is associated with considerable losses of heat, it is not adiabatic, which is formed with a residence time of about 3-7 minutes , would lend about 6.5 kg of the Äthyleh-Propyien-Cöpöiymer ^ n * is passed, the copolymer formed in the Kebengefäß i lich.eiher zone, in which ¹ is the. mixed in the reaction product haup tube formed wiidj Gie'i§h "-.. time it takes for a sample of the Äthyien-Fropylen-Ö'öpolyrieren 'estzweeken; ¥ ie the iPrüfuhg showed it has eiile" cSchmeiZfluBViskositat O of ₅₀₈₆ dg / ain * wiiä eihö. Density of öjS04 g / öm i äis contains ■ about 1 & GeWiH p & lyme-s. rized propylene and ■ in the Polyiaer'enkette

e 52 methyl groups hs.

Simultaneously passing in da-s was charged with isooctane and 15ö ° G kg at a pressure of about 32.5 / cm reaction vessel held the Hauptpolymerisationszone hourly from 27 _S '6 kg ethylene j 0 ^ 03 kg and 195 kg wat isooctane existing A mixture of monomers is used and about 32 kg of the lysaxor dispersion is added continuously every hour. It runs adiabatic than the implementation in the next _vessel% although her 'the ¥ har · ^ meverluste are still significantly * There hourly forms at a residence time of about 180 minutes about 2 to 3.1 kg of polyethylene. A sample of the polyethylene is taken for test purposes, as the test shows, it has a melt flow viscosity of 9 dg / min and a density of 0.967 g / cm. The polyethylene formed in the main vessel is also fed continuously to the mixing zone mixes it with that here

209884 / 126H

© AD ORIGINAL

herkommenden from branch vessel copolymer at a temperature of 150 ⁰ C, which is above the Fällpunktes the two polymers. The two polymers are here dissolved in isooctane. Mixing is effected by means of turbulent flow, by running the solutions of the two polymexes through a conduit or pipe. The two reaction mixtures are added in such a proportion that the mixture contains about 22 parts by weight of the ethylene-propylene copolymer and 78 parts by weight of the polyethylene on a dry basis.

The isooctane solution containing the polymer mixture and residues of the catalyst is treated in a known manner Way, i.e. the catalyst is inactivated by adding isopropanol, the catalyst residues are removed and separates the polymer mixture in the molten state from the isooctane. The polymer mixture has been purified and isolated a density of 0.956 g / cm; and a melt flow viscosity of 3.0 dg / min. It contains, on its weight based, - ^ 3.6 wt.% polymerized propylene. One checks a sample of the mixture (sample no. 1) for stress corrosion resistance, impact strength and processability, The test results are given in Table I.

For comparison purposes, in order to demonstrate the progress established by the invention, an ethylene polymer of the usual type is produced which has approximately the same density and the same processability as the above-mentioned polymer mixture. Only one reaction vessel is used in the production of this polymer and it is operated under conditions which, with the exception of the fact that propylene is added to the monomer mixture, correspond to the conditions used in the main vessel of the process according to the invention (sample no. C ₁ ). This sample is also tested for voltage and corrosion resistance , Impact strength and processability tested. The results are also given in Table I.

209884/1282

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Examples 2 .bis ,. 4th

Kan represents in the examples. Z and, 3 after dam.id example. 1 described Pärailelverfahren. two more: Mixtures according to the formulations and conditions mentioned in Table II (tests 2 and 3) and tests the obtained: Polymer mixtures using samples 2 and 3 for their melt flow viscosity, their density, their processability, their impact strength and their stress corrosion resistance . The test results are recorded in Table III.

In Example 4, according to the recipe and under the conditions that are also mentioned in Table II, a polymer mixture is produced by the step process / According to this process, the monomer mixture containing ethylene and propylene is introduced into the secondary vessel and polymerized therein to the above conditions, the copolymer formed passes continuously into the liauptgefäß, it mixes therein with further Konoir.eren and another catalyst and then carrying out the polymerization by aas mixture under the conditions mentioned. Kari releases the polymer mixture that forms and tests it for: its density, processability, impact strength and resistance to stress corrosion (sample no. 4) * The test results are listed in Table III.

2u VaVjleiehszv.'wOken and to show how essential in According to the invention, the concentration of the alpha-olefin comonomer is in the high molecular weight fraction is adjusted according to the procedure described in Example 4 Polymer mixture here, the polymerized in the main reactor Medium molecular weight fraction has a far higher propylene content than that in the side reactor polymerized high molecular weight fraction. The used Monomers and the conditions under which the comparative polymer mixture are listed under A in Table II. The mixture is released and tested

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BATH ORIGINAL

it depends on its viscous flow viscosity, density, processability speed, impact strength and stress corrosion resistance (Sample A). The test results are given in Table III

ι listed. ·. "·" -

2O988A / 12R2

Table II

so ο «ο

Attempt no .

Secondary factor temperature, ⁰ C pressure (kg / cm ² ) monomer mixture (.kg / h) ethylene propylene is © octane catalyst additive (kg / h)

Dwell time (min.)

Amount of polymer produced in the secondary reactor (kg / h)

Main reactor temperature, ⁰ C pressure (kg / cm) Monomer mixture (kg / h)

Reaction mixture from the

Kebenr eactor

Ethylane

151 1:53. 150 150 5 32.5 32.5 32.5 32, 80 9.06 10.19 13.59 6, 72 10.42 4.98 2 ,, 72 2, , 11 190.71 , 187.09 186.64 182 01 0.03 0.02 0.01 0, 17th 17th 17th 18th

7.70

7.70

5.89

150 146 150 150 KJ 32.5 32.5 32.5 ' 32.5 CO
CD
89 O O 202.94 '191.62 27.63 27.18 23.10 30.80 O O 0 0

Experiment no. ·

Hydrogen IsoQctane '■ · Catalyst addition (kg / h)

Dwell time (rain.)

Amount of that produced in the main reactor Polymers (kg / h)

O , 02 O, 01. O , 04 O , 02 212 i OO 185 28 193 , 43 193 , 43 O , 28 O, 45 O , 16. O , 29 168 190 .91 97

25.37

24.46

28.54

30.35

The trials in the A and 4 over-run from the secondary reactor into the main reactor
Mixture (202.94 or 191.62 kg / h) consists of isooctane, unreacted ethylene
and propylene and polymer formed in the side reactor.

Table III

Sample composition of the polymer

Propylene Melt Melt Density Processing IZOD Voltage

behavior- flußvis- flußvis- (g / cm · ⁵ ) ability (2) · impact resistance- corrosion-

nis (5) kosity, kosity- (Poise at. strength. strength

of the Gemi- behavior- I9OOC and, (3) (4) (h)

sches (l) nis (6) 1000 sec.) (I (dg / min.)

1000 sec. ~ ^X ) (kg.-m / cm)

76% PÄ (f) 24% Ä / Pr (g)

74% PÄ (h) 26% Ä / Pr (i)

83% Ä / Pr

83% Ä / Pr (5} 17% A / Pr (k)

* 4 84% Ä / Prfl) 16% 1 / Pr (D)

15 37

3250 3000

0351 2350 0.960 2200 0.956 2080

0.957

2120

0.18 0.10 0.03 0.04

(f) Polyethylene having a melt flow viscosity of 5 dg / min and a density of 0.967 g / cnr ';.

(g) ethylene-propylene copolymer (75.1: 24.9) with a melt viscosity of

"X ·

0.33 dg / min., A density of 0.896 g / cm and a degree of crystallization of

<^ 19%, determined with a differential calorimeter;
(h) Polyethylene having a melt flow viscosity of 4 dg / min 'and a density

of 0.966 g / cm "; '. ■

(i) Ethylene-propylene copolymer (93.4: 6.6) with a melt viscosity of

■ 0.011 dg / min., A density of 0.926 g / cm and a degree of crystallization of , definitely with. a Dj, ferential calorimeter;

360 1 100 to
1 20th 23

CJ <D GO U)

, (, j) Αΐ ^ γ1βη-ΡΓορ7ΐΘή ~ ϋορο1γΐη '& Γΐ3 · Εΐ (98.5: 1 * 5) - with a melt flow viscosity of 13 dg / min, and .a "density -of 0.93S g / cTT:; '.' ■

(k) Ethyleii-Prbpylen'-Copolymeri-sarb '{98.2: 1.8;) with a mold flow viscosity of 0.04 dg / rriin.j a density of' _} 9 ^ '3 g / cm - and one ,; Er.istallls, at, lo: nsg: rad. from ^; * y '(&%,' determined iniit a blfie: r'Bn; t.lalkalDriin ^; eter :;.

9 dg / min, and a piclite ^ on D, 956 g / cm ^ ;;

(m) Atiiyleri-propylene copolymer ^: 96.7: 3., 5: 1 with an average viscosity of 0.003 dg / min, a weight of 0.935 g / cm and a degree of crystallization of

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360-CO

Example 5

According to Example 1, several polymer mixtures are also prepared a high propylene content in the high molecular weight fraction (samples 1 to 3). The mixture is released and tests them for their melt flow viscosity, density, processability and impact strength. "The results of the test are listed in Table IV.

For comparison purposes, several polymer mixtures are prepared in the same way, the high molecular weight fraction of which does not have a high propylene content (samples B-, to B ·,). After they have been released, these mixtures are also tested for their melt flow viscosity, density, processability and impact strength. Also the results of this. Tests are recorded in Table IV.

209884/1262

Table IV

Sample together- propylene- propylene- · propylene- melt density processing-. IZOD

meeting of the salary of the. y receives-. flow vis- ibility (2).

Polymeric high molar fraction of (5) viscosity. mix (Poise at ability

kularen with mean (g / cnr) 190 ° C and '(kg, -m / cm)

Fraction lerem Mo- misches 1000 sec. " ¹ )

(SO (7) lekular- .. (1)

weight (dg / min,)

B,

Pl

22? Ό A / Pr (b) 16 0 63? F Ä / Pr (c)
Ä / Pr (d) 1.8 1.5 PÄ (e) 16 0 % Ä / Prif)
A / Pr (d) 1.8 1.5 ^r 7QC * '
( O / 2
22% Ä / Pr (b) 16 -0 Ä / Pr (h>
Ä / Pr {d) 1.8 ■ . 1.5

OO

1.2

1.2

1.2

2.09 0.956 2790

0.952 2450

2.97 "0.9565 2250

3.51 0.956 2080

5.19 0.959 1620

11.62 - "■ 0.958 € 108

0.28 0.05 0.19 0.03

0.06 0.02

(a) Polyethylene has a melt flow viscosity of 8 dg / min .. _: and a density of 0.967 £ / cm ³ :

(b) 'Äthyleri-Fröpylen copolymer (84:16) having a Schmelzflußviskosität of 0.086 dg / min, and a ¹ Jq Ij) Ielite of 0.904 g / cm ^; · ■■ S

K) U) CJ

03> O

3 ο ; ζ

(C) ethylene-propylene copolymer (38.5: 1.5) with a melt flow viscosity of

8 dg / min, and a density of 0.956 g / cm; · ·

(d) Ethyl ^ propylene copolymer (98.2: 1.8) with a melt flow viscosity of . 0.004 dg / min, and a density of 0.9 ^ 3 g / cm;

(e) Polyethylene with a melt viscosity of 9 dg / min, and a density of ■ '■■■ 0.967; g / .cffi2;

(f.) ethylene / propylene copolymer (98.5: 1.5) with a melt flow viscosity of 13 dg / min, and a density of 0.956 g / cm;

(g) Polyethylene with a melt flow viscosity of 13 dg / min and a density of 0.968 g / cm ^!

ίο (h) ethylene-propylene copolymer (98.5: 1.5) with a melt flow viscosity of.

5 ^; +9 dg / min, and a density of 0.959 g / cnr.

^ n ₁ . ro

-α In Table IV, the digits (1) to (3) and (5) have the same meaning ^

is? ■ ι

a »as in Table I. Also indicated.

*** ■ '(7) in percent by weight the content of the high molecular weight polymer fraction of polymerized Propylene and. ". ·. ■

(8) in percent by weight the content of the polymer fraction with an average molecular weight of polymerized propylene.

U) W CD CO OJ

Claims (1)

1. A solid, homogeneous and highly impact-resistant ethylene polymer mixture of high strength under normal conditions Density, characterized in that there is a larger amount of an ethylene polymer or one made of ethylene and an alpha-olefin comonomer consisting of • -polymer of medium molecular weight.and high density and in a smaller amount of at least 3% by weight of the mixture is a high molecular weight, non-elastomeric copolymer consisting of ethylene and an alpha-olefin with a crystallinity of at least 5% and a content of alphar-olef imnonomerem from 2 to 40 GeM,% of the copolymer contains, where the high molecular weight copolymer: (1) Has a melt flow viscosity not higher. is than one fifth the melt flow viscosity of the medium molecular weight polymer and (2) has an alpha-olefin monomer content that is at least three times as large on a weight basis as. the amount of in the medium molecular weight polymer contained alpha-olefin monomers 2. Mixture according to claim 1, consisting of (A) at least 60% by weight of an ethylene polymer with its own Average molecular weight, based on up to 6% by weight of a polymerized "aliphatic contains alpha monoolefins with 3 to 12 carbon atoms and a density of 0.945 to 0.970 g / cm? and a melt flow viscosity νοη 0.5 to 500 dg / min, has, and - .. "-. (B) 5 to 40 wt. % Of a high molecular weight, • non-elastomeric copolymer produced from an alpha-olefin, which is based on 2 to 40 wt. . merized aliphatic alpha-monoolefins κit 3 to contains carbon atoms and a crystallinity of at least 1Q%> a density of 0.870 to 0 ^ 955 -g ^ 209884/1202 and a melt flow viscosity of 0.0001 to 6 dg / min, has, the high molecular weight copolymer (1) Has a melt flow viscosity not greater than the tenth part of the melt viscosity of the medium molecular weight polymer and (2) Has an alpha-olefin monomer content equal to • The weight base is at least ten times greater than the ■ . Amount of alpha-olefin monomers contained in the medium molecular weight polymer and where the Mixture based on a content of 0.5 to 15% by weight of alpha-olefin monomers, a melt flow viscosity ; sity from 0.2 to 20 dg / min, and a density of 0.940 up to 0.967 g / cnr. 3. Mixture according to claim 2, characterized in that the ethylene polymer with an average molecular weight Is polyethylene. 4. Mixture according to claim 1 to 3 »characterized in that that consisting of ethylene and an alpha-olefin high molecular weight copolymers is an ethylene-propylene copolymer in which the proportion of the copolymerized Propylene makes up 2 to 20% by weight. 5. Mixture according to claim 4, characterized in that it has an IZOD impact strength of 0.28 to 0.06 kg.-m / cm, a density of about 0.951 to about 0.960 g / cm and has a melt flow viscosity of 1.8 to 5 »19 dg / min. 6. Process for the production of an under normal condi- . solid, homogeneous and highly impact-resistant ethylene polymer mixture of high density, characterized in that one (l) ethylene or a mixture of ethylene and an alpha-olefin comonomer in a solvent and in the presence of a Ziegler catalyst for solution 209884/1262 2233S83 . polymerization polymerized in a Hauptζone eignem under such a pressure that forms in the essential ■ 'chen no vapor phase; ■ (2) ethylene and an alpha-olefin in a solvent in the presence of a Ziegler catalyst hot solution ■ polymerization temperature copolymerized in a sub-zone under such a pressure that essentially ■ lent no vapor phase forms, · -. "·. the polymerization in the first zone and the copolymerization in the second zone being coordinated with one another in such a way that _; ' (A) the copolymer obtained in the sub-zone is a Melt flow viscosity of not more than one fifth the melt flow viscosity of the polymer obtained in the main zone and '· (B) the copolymer obtained in the sub-zone has a content of alpha-olefin comonomer on a weight basis is at least three times the alpha olefin monomer content of the polymers obtained in the main zone »and (3) those obtained in the two polymerization zones Products in the liquid state in such a proportion summarizes that the product of the main zone makes up the bulk of the mixture. 7. The method according to claim 6, characterized in that ■ the polymerization in the main zone and the copolymerization in the secondary zone are carried out at the same time will. 8 »Process according to claim 6, characterized in that the polymerization in the main zone and the copolymerization in the secondary zone follow one another in the manner. be carried out that at least part of the reaction chamber of one zone is passed over into the other zone and the polymerization is initiated in this zone, wherein the reaction mixtures of the two zones supple Quantities of the Ziegler catalyst are added. ·. ' . ' 9ν method according to claim 8, characterized. ,, that at least part of the reaction mixture is initiated in the Kauptzone the side zone and the polymerization was continued in this. _> . 10. The method according to claim 6, characterized in that one (l) in a main polymerization zone an 85 to mol? o ethylene and 0 to 15 mol? » an aliphatic alpha-monoolefin-containing monomer stream in an inert liquid diluent and in the presence of an amount of hydrogen from 0.1 to 5 MolSä of the total amount of the monomers contained in the monomer * fcrom and a catalytic amount of a Ziegler catalyst at a temperature of 120 to 220 ⁰ C and under a pressure of 10 to 50 atm. polymerized; that he • (2) in a secondary zone a 60 to 90 MoIJa ethylene and 10 to 40 MoIJo of an aliphatic alpha-IIonoolefin containing second monomer stream in an inert liquid diluent and in the presence of a catalytic amount of a Ziegler catalyst at a temperature of 120 to 220 ° 10 to 50 atm C and under a pressure ^ ron. polymerized, the polymerization • in the first zone and the polymerization in the second Zone are coordinated in such a way that (A) the polymer obtained in the sub-zone a Melt flow viscosity of not more than one tenth of the melt flow viscosity of that obtained in the main zone (B) the polymer obtained in the sub-zone has a content of aliphatic alpha-olefin monomer which is at least about ten times as large on a weight basis like the amount, of the aliphatic alpha-olefin monomer, which contains the polymer obtained in the main zone *, and that one 209 8 8 4/1262 (3) the solutions in the two polymerization zones polymerization products obtained together in a quantitative ratio that the mixture of at least 60 Gew.ίό of the polymer obtained in the main zone and from 5 to 40 Gev /. ^ of that obtained in the sub-zone Polymers is made. 209884/1262