DE3043949A1 - BLOCK MIXING POLYMERIZATION METHOD AND PRODUCT - Google Patents

Description

PATENT LAWYERS

l · Dr. V. SCH MIED-KOWARZIK
Dipl.-Ing. G. DANNENBERG Dr. P.WEINHOLD Dr. D. GUDEL

335024 SIEGFRIEDSTRASSE 8 TELEPHONE: C089) _4Q

Case: EP-3OO4 Wd / Wd

El Paso Polyolefins Company W. 115 Century Road Paramus, New Jersey 07652 / U. S, A.

BLOCK MIX POLYMERIZATION PROCESS AND PRODUCT

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In the case of block polymerization, essentially a combination]

nation of the best physical and chemical properties i obtained two or more polymers, e.g. B. the combination ^

_s those properties of polypropylene with those of polyethylene. While polyethylene does not have as high a melting point or tensile strength as polypropylene; on the other hand, it has excellent properties at low temperatures such as. B. with regard to brittleness and impact \

κ, strength. If the excellent properties of these; If both polymers are combined in the process of block polymerization, a heteropolymer is obtained, which

can be used for many fields of application for which j neither homopolymer was practical.

is j

A group of block copolymers that have excellent physical \

Has kaiische properties are the ethylene-propylene- I

Block copolymers such as B. those of the P-EP type, where P is an i

Iropylene homopolymer bloom and EP denotes an ethylene j

Propylene post-block of the copolymer is. By varying j

the proportions of the block polymers and the polymerized =

The physical properties of the ethylene content can be good j

regulated to suit the particular application, I.

for which the polymer product is intended. In general, 'is the room temperature -Schlagfestigkeit of block copolymers directly proportional at constant melt flow essentially the amount of polymerized ethylene

in the overall product. :

Block copolymers are advantageously produced on an industrial scale by the process described in US Pat. No. 3,514,501. Briefly, this process comprises the manufacture of: a billet, preferably in the liquid phase; catalytic polymerization of propylene in a carbon _; hydrogen diluents such as. B. liquid propylene j to form a slurry. After separating the! slurry becomes the prepolymer that still has residues of active? vem catalyst contains, in at least one reaction zone; introduced, in which it is sufficient with monomer vapors *

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the period of time is reacted to form the post-polymer block on the prepolymer block in the desired proportions. :

The conventional catalyst system used in the past for such polymerization processes is; from an unmodified one or one with an electron »- r donator-modified titanium halide component, which is made with

an aluminum-organic cocatalyst is activated. 10 Typical examples of conventional polymerization ^catalyst:; Systems for propylene include cocrystallized titanium tri-; chloride / aluminum catalysts of the general \ formula n.TiCl., .AlCl- activated with diethylaluminum chloride and triethylaluminum. The co-crystallized Titantrichloridj ₁₅ aluminum may have been subjected to a Elektonendonatorverbindung to enhance its activity or stereospecificity modification treatment \. Such compounds include phosphorus compounds, esters of inorganic and organic acids, ethers, and numerous other compounds.

A major disadvantage of using the aforementioned conventional catalysts is the low catalyst productivity, what the need for subsequent ash removal from the product makes necessary to reduce the proportion of catalyst residues that would otherwise degrade the product quality would affect.

Recently there are new ones for the polymerization of C * -01efins Catalysts have been developed that are far more active

than the aforementioned conventional catalysts. In short ■ these catalysts consist of a titanium halide

Catalyst component supported on a magnesium dihalide and an alkyl aluminum compound which may be present as a complex with an electron donor compound.

These catalyst components are in the literature, for. B.; has been described in: US Pat. No. 3,830,787, 3,953,414, 4,051,313, : 4,115,319 and 4,149,990.

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The productivity values obtained with these new catalysts are extraordinarily high, so that polymers can be used obtained that contain so little catalyst residues, ■ that the conventional step of ash removal can be omitted. The catalysts are used in homopolymerization of propylene and in copolymerization of a mixture of propylene and another ^ -olefin such as B. Ethylene is effective provided that the polymerization reaction

κι in a liquid diluent such as. B. liquid Propylene monomer takes place. In vapor phase polymerization, which are used in the production of the EP copolymer block of the P-EP block polymers (as described above) conventional process conditions is used

, r, however, found that the product quality of the obtained Block polymer is practically bad. In particular, it has been found that - to achieve the desired impact strength in the To achieve the desired melt flow - considerably more ethylene must be incorporated into the overall polymer than

_{? ()} This is the case when conventional catalysts are used. The need to increase the ethylene content to achieve impact strength adversely affects other desirable properties of the end product such as: B. stiffness, dimensional stability under heat, tensile strength

_{? u} etc.

It is therefore an object of the present invention to provide a highly effective process for the vapor phase polymerization of ethylene / propylene blocks onto preformed propylene polymers _{J ()} which results in polymer products with improved impact strength without significantly affecting other desirable physical polymer properties.

Another object of the invention is to provide a process for the preparation of ethylene / propylene block copolymers in which the polymerized ethylene content of the total polymer product is brought to a minimum _r in order to obtain the desired impact strength.

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Another object of the present invention is to provide a new ethylene / Fropyleu block copolymers, which as compared with conventional ethylene / propylene BlockmiGch ^r, with the same polymeric Geyamtäthylengehalt improved Verarbnit harke it during the extrusion or injection molding has.

Another object of the present invention is that Creation of a new ethylene / propylene block copolymer, in which at lower extrusion or compression molding temperatures and / or lower extrusion or compression molding pressure than conventional resins with the same melt flow and the same Ethylene content can be processed.

The invention relates to a continuous vapor phase block copolymerization process which includes the following steps:

_{? i)} (A) Preparation of a preformed propylene polymers in particulate form, wherein the preformed polymer ^back: Scores of active catalyst and being prepared by polymerizing propylene in the presence of a catalyst composition comprising the

. _J5 contains the following components:

a) an aluminum trialkyl compound or an aluminum trialkyl compound which is at least partially a complex formation with an electron

_{3 ()} donor compound has been subjected and

b) titanium tri- or tetrahalide on a magnesium dihalide support,

or a complex of Titantri- or tetra- \ holagenids with an electron i on a magnesium dihalide; \

(B) introducing the preformed polymer into at least one j continuous, stirred reaction zone; j

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(C) Introducing ethylene and propylene monomers into the Reaction rate in a molar ratio of ethylene to Propylene from about 0.15 to about 0.3 and

(D) polymerizing the ethylene and propylene monora in the Vapor phase in the reaction zone on the preformed

Propylene prepolymer.

in the description and claims of this invention the following terms have the following meanings:

a) "preformed polymer" means a propylene polymer; which is suitable for independent use, which

v, but back;.; contains land of active catalyst.

b) "Active catalyst residues" means catalytic Components in the polymer that cause the polymerization of added monomers, with the addition of further amounts of catalyst is not necessary. The active catalyst residues mentioned here are preferably those as in the initial polymerization used to make the preformed polymer.

c) "Block polymer" has the same meaning as it after State of the art is common, d. H. consists of a polymer molecule

_{? fi} from a single section of one oC-olefin polymer or copolymer bonded to a single section of another <* - 01efiri polymer or copolymer. Block polymers comprise two or more mixed polymers, these being polymerized one after the other,

. _{! n} and eiti homopolymer, followed by a mixed polymer

or, alternatively, homo- or mixed polymer blocks of two or more «'-olefin monomers.

d) "Volatile ingredients" include non-polymerized ones CO-01efin monomers and inert hydrocarbon diluents; medium such as B. ethane, propane, butane, pentane, hexane, heptane,

Octane, aromatic hydrocarbons, diesel oils or the - ! same. 1

e) Polymerization in a "hydrocarbon diluent" means that the polymerization can be carried out in the presence of inert carbon j hydrogen diluents such as ;

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3Q43949

ζ. B. in the presence of those mentioned above under d) or polymerizations, wherein the tlonomcr, z. B. propylene, while maintaining appropriate temperature and pressure conditions is kept in liquid form during the polymerization and itself serves as a dispersion medium or mixtures of inert hydrocarbons and olefin monomers are used in liquid form, f) "vapor phase" block polymerization and "essentially

in dry prepolymer "means that a preformed polymer, that contains volatiles on the order of about 5% or less, with gaseous monomers without Addition of inert hydrocarbon diluents is implemented.

_T propylene optionally mixed with minor amounts of other c ~ £ 01efine be used with about 2-10 carbon atoms or more, to form a prepolymer. The other olefins are e.g. B. ethylene, 1-butene, 1-isobutene, 1-pentene, 1-hexene and higher compounds and branched-chain (^ -olefins such as 2-methylbutene-1, A-methylpentene-1 and higher compounds. Of these Monomers, propylene and mixtures of propylene and ethylene are particularly interesting and preferred.

_{? l>} it is preferably to a concentration of about 0.3-2 wt .-% of the total monomer charge limited.

The prepolymer is formed in the reaction zone using a hydrocarbon diluent and a polymerization _catalyst , the polymerization being carried out to a solids content of about 5-60%, preferably about 20-40%. The preferred diluent is liquid propylene.

In a preferred embodiment of prepolymer formation, d. H. in the well-known so-called "liquid pool process", the propylene functions both as a liquid diluent as well as reactants, with small! 'narrow inert hydrocarbons such. B. hexane, mineral oils,

,Paraffin
liquid etc. leading to the introduction of the catalyst component

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can be used in the reaction zone
can.

The reaction is continuous. The monomer feed and the catalyst components are fed continuously into the reactor
given and a slurry of polymer product and
liquid propylene is withdrawn, preferably by means of a cyclic withdrawal valve, which the continuous

simulated in operation. Various modifiers such as
z. B. Hydrogen can be added to change the properties of the polymer product. Such modifiers are known to those skilled in the art and are intended here
cannot be further described as it is not part of this

_{15 are} invention.

As the catalyst components used in the present invention
Any of the recently developed, highly active supported magnesium halide catalyst components and organoaluminum cocatalyst components such as those described in US Pat have been used,
express reference is made to the disclosure of which here.

Such a catalyst composition is typically: a two-part composition, wherein the components \ separately be added to the polymerization reactor. Preferably, component a) of such a composition comes from the group: trialkylaluminum with 1-8 carbons:

material atoms in the alkyl group such as. B. triethyl aluminum, trimethyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, triisohexyl aluminum, tri-n-octyl aluminum and triisooctyl aluminum. The trialkylaluminum is particularly against the \ introduction into the Polymersiationsreaktor with an electron}

... the donator is subject to complex formation. The best results are achieved, x ^ enn esters of carboxylic acids or diamines, in particular esters of aromatic acids, can be used as electron donors *. !

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Some typical examples of such compounds are methyl;

and ethyl benzoate, methyl and ethyl p-methoxybenzoate, di-; ethyl carbonate, ethyl acetate, dimethyl maleate, triethyl borate,

Methyl o-chlorobenzoate, ethyl naphthenate, methyl p-toluate, ethyl toluate,

Ethyl p-butoxybenzoate, ethyl cyclohexanoate, ethyl pivalate, \

N, N, N ', N'-Tetramethylenediamine, 1,2, A-Trimethylpiperazine,: 2,5-dimethylpiperazine and the like. The molar ratio

from aluminum alkyl to electron donor can be between about;

, o 1-100, preferably between about 2-5. Solutions ; the electron donor and the trialkylaluminum compound

in a hydrocarbon such as B. hexane or heptane ■ are preferably for a period of time, in general

for less than 1 hour before introducing the mixture into;

the polymerization reaction zone reacted. =

The other component of the catalyst composition is \ either a Titantri- or -tetrahalogenid on a J magnesium dihalide or a complex of a Titantri-!

or tetrahalide and an electron donor compound j on a magnesium dihalide support. The halogen in the \ respective halide may be chlorine, bromine or iodine; j the preferred halogen is chlorine. The electron donor
- if this is used in complex formation -

appropriately comes from the group of the inorganic esters
and organic acids containing oxygen and the polyamines. Examples of such compounds are the esters of aromatic carboxylic acids such as. B. benzoic acid, p-methoxybenzoic acid and p-toluic acids and especially the alkyl esters
named acids; the alkylenediamines such. B. N ¹ , N ", N"', N ¹ " ¹
Tetramethylethylenediamine. The molar ratio of magnesium
to the electron donor is about 1 or more, preferably between about 2 and 10. The titanium content (calculated as
Titanium metal) is generally between about 0.1 and
20% by weight in the supported catalyst component, preferably
between about 1 and 3 weight percent.

The production of such supported catalyst components is

has been described in the literature, and these are

available on the market. S.

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In specific embodiments of the invention, as Electron donors used carboxylic acid esters, which are about

I to 2 carbon atoms in the ester group and about 1 to

II contain carbon atoms in the acid component, while the diamines which can be used as electron donors preferably contain about 4 to 7 carbon atoms.

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- - «ΓThe catalyst components a) and b) are in such Amounts introduced into the prepolymer reaction zone that the Al / Ti molar ratio are in the wide range of about 1 to about 10,000, preferably between about 10 and 200, is maintained.

The temperatures at which the prepolymer takes place are known in the prior art and are, for. B. between 10 ° and 121 ° C, preferably between about 46 7 ^ ⁰ C, in particular between about 52-68 ° C. The pressure in prepolymer formation can be from atmospheric pressure or below at which normally liquid, inert hydrocarbon diluents such as. B. heptane or hexane can be used up to a pressure of 35 atm

or more, in which propylene as its own dispersant or propylene in mixture with a normally gaseous hydrocarbon diluent such as. B. propane or butene, which _{are liquid under the reaction conditions S 20} , are used.

j The prepolymer is converted from the reaction zone to an ab-! ; separation zone such as A cyclone or a bag \ filter passed example, where the volatile constituents of the ^\! ₂₅ polymer separated and further processed by known methods and returned to the reaction zone. The: the volatile constituents are separated in sufficient quantities; : to the extent that less than about 10%, preferably no more than about 5% volatile content remains in the prepolymer.

In the case of gas phase bulk polymerization, the polymer that is recovered from the separation zone and the residues accumulate contains active catalyst, passed into a continuous stirred 'reaction zone which is equipped so that the Ethylene monomer and the propylene monomer at one or more points along the length of the zone (and inert gases such as B. nitrogen) can be introduced so that the residues of active catalyst in the prepolymer polymerize said monomers to a block, whereby the

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- nrr-

final properties of the resin modi \ prepared are sheet. The polymerization in the continuous stirred reaction zone is generally carried out at a pressure performed below that used in the prepolymerization pressure, namely at about 0.7 - 3.5 ^atmospheres: or slightly more. The polymerization temperature can, for. B * in the range of about 10-99 ° C, preferably 54-93 ° C. _s

:

The ethylene and propylene monomers must be mixed before introduction into the gas phase zone. It is ^; even advantageously, each monomer separately at one or ^; preferably several points along the reactor lead _1f) . Liquid propylene can be introduced which, when evaporated, removes part of the heat generated by the polymerization in the reaction zone. The mole \ ratio of the introduced to the reaction zone throughout the entire j ethylene to propylene, however, should be from about 0.15 to 0.3 ⁺ are maintained. When using higher proportions; It has been found that the effectiveness of the ethylene content in the overall polymer product on impact strength properties is significantly reduced. For example, it is \ at a molar ratio of 0.5 required about introduce double the amount of ethylene in the whole polymer to the same impact values to obtain \ product as a final reagent prepared with a ratio of about 0.2 became. _;

In general, in the entire block polymerization

reactor system between about 5 - AO wt .-% block polymer, based on the weight of the total polymer produced, produced =

Include appropriate, continuously stirred reaction zones

those described in US P 3,514,501, the disclosure of which is expressly incorporated herein by reference. The reaction zone can consist of one or more tubular reactors arranged in series, optionally with a jacket for dissipating the heat and suitable introduction

⁺⁾ ie 0.15-0.3 Hol, ft £ hvle_n dio MpI propylene

openings for the monomer and with a stirrer; be equipped. According to a preferred embodiment according to the invention, one or more horizontally;

■ 5 Ie ribbon mixer reactors for continuous operation

{ used. Such reactors come with a number of inside ^; _; Belt blades and / or blades equipped, which rotate due to: a power drive. With a suitable arrangement of the stirring device, the polymer can be passed continuously from the inlet to the outlet. Independent of stirring or mixing _:

During the process, the polymer powder behaves essentially very similarly to a flowing medium and "flows" or moves

■ move from the entry point of the reactor to the starting point,

; d. h, it flows along the entire reactor length in a manner similar to a flowing medium such as a ^liquid: ness.

; ,at least

; Propylene is introduced ⁷ through the reactor inlet port,

: When using liquid propylene monomer, the Feed preferably through inlet spray nozzles along: the top of the reactor. The ethylene monomer feed in vapor form can be done in a similar manner at points along the length of the reactor. It is an advantage if the 'The reactor has an outer cooling jacket around the Dissipate heat through the reactor wall. Optionally, additional vapor phase reactors can be installed in series with the bulk polymerization reactor be arranged to increase the residence time. If necessary, can - depending on the desired Purpose - various known modifying agents are added to one or more of the reactors.

Because of the high productivity of the supported catalyst system (given in kg of polymer produced per kg of Ti metal) - and the productivity has been further increased according to the invention, there is no need for a step of ash removal to remove the catalyst residue from the polymer, as is the case with conventional catalysts,

: The polymer products according to the invention, which with the help of the

preferred "liquid pool" process. have the following properties: -

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: -yes · - ί

'■ Your melt flow range is between about 0.1 and 10 g / 10 min.

ratio of weight average molecular weight to number average f

Molecular weight is over 6.5, the ethylene content is / e ^ ä ^s f ^ W. -%,

> 5 preferably more than about 4% by weight, the titanium content is not higher than

about 3 ppm, the Mg content not higher than about 40 ppm, the Cl content |

no greater than about 100 ppm and the total ash content is i

no higher than about 400 ppm. \

id The particular advantages of the polymers according to the invention \

Compared to conventional polymers include: one,

wider range of processability, lower energy \

needs in processing, better ability to fill \

thin sections and numerous indentations in the shape, J

better deep-drawing properties and easier drawability j

as well as higher processing speed in the manufacture of j

production of filament and staple fiber products. \

Based on spiral melt flow measurements, z. B. j

found that the polymers according to the invention with a j Melt flow range of about 2 -IOg / 10 min. At press temperature,

the 23 - are about 17 degrees lower or Druckver-. \

2 *

conditions that are approx. 25 - 11 kp / cm lower are processed!

can be compared to conventional polymers with j

_{or the} same melt flow (ASTM-1238) and the same total ethylene \

salary is the case. Ϊ

It is believed that the molecular weight distribution of;

Mw / Mn is the property that is most likely i

Improvements in impact resistance as well as rheological j

see values of the polymer and the processability \

brings. Polymerization using a conventional catalyst \ system typically gives a polymer product with a

Ratio of Mw / Mn of at most 6.5, generally j

of less than 6, while the inventive polymers J

j

a ratio of Mw / Mn of at least 6.5, in particular I.

about 7 to about 10. :

If necessary, various J

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I REQUIRED

-; μγ-

Additives such as fibers, fillers, antioxidants, metal deactivators, Heat and light stabilizers, paints, pigments, lubricants and the like can be incorporated.

The polymers according to the invention can advantageously be used in the production of fibers, threads and films by extrusion, in the manufacture of rigid objects by injection molding and in the manufacture of bottles by blow molding processes be used.

The following examples illustrate the advantages of the invention.

Examples 1-7

The tests were carried out in a continuously operated pilot plant on an industrial scale. To prepare the prepolymer, a reactor equipped with a stirrer was continuously charged with propylene and the catalyst components, the rate of monomer charging corresponding to a residence time in the reactor of 2 hours. The organoaluminum compound of the catalyst system was a hexane solution of triisobutylaluminum (TIBA) which had been treated with a hexane solution of methyl p-toluate (MPT), an electron donor compound, before being introduced into the reactor. The solid titanium halide catalyst support component was a commercially available catalyst. The catalyst support component contained about 1.5 weight percent titanium, 20.3 weight percent magnesium, 60 weight percent chlorine, and 9.6 weight percent volatile hydrocarbons . Ethyl benzoate was used in the preparation of the catalyst support component. The two catalyst components were introduced at a rate which was directly proportional to _r of the polymer production rate and in amounts sufficient to maintain the polymer solids concentration in the reactor slurry at a nominal value of about AO%. The catalyst productivity (kg polymer / kg Ti metal) was determined in each case from the removal rate of the polymer slurry, the solids

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content in the slurry and the amount of titanium analyzer component added calculated.

_ö After separating the prepolymer from the unreacted propylene this prepolymer, which still contained residues of active catalyst was subsequently arranged in two series, equipped with a jacket for water cooling, directed horizontal reactors wovQn each of the reactors with ribbon blades for the purpose of stirring was equipped. The propylene was introduced near the opening of each of the reactors, the ethylene through three openings evenly distributed over the reactors. The block polymer product was recovered from the outlet of the second reactor. The process conditions in each of the reactors were essentially the same unless otherwise indicated. The respective process conditions and results are given in Table 1. The drawing shows the ratio of Gewoi ethylene in the product to the Izod-

Notch toughness (at room temperature). Curve A denotes the typical ratio that is found in the manufacture of the Pre-polymers obtained with conventional catalyst such. B. Stauffer AA catalyst (3TiCIo.AlCIo) with diethylaluminum chloride as a cocatalyst (Al / Ti molar ratio = about 3) and under conditions that result in a final product melt flow of about 2g / 10 min. allowed. It has been found that in such a conventional method, that used The ethylene / propylene molar ratio in the vapor phase reaction zone can be varied considerably, e.g. B. from

about 0.2-0.8 without significantly affecting the relationship represented by curve A.

Curve B describes the ratio of ethylene content to Izod impact strength, which is determined according to the

same examples 1 - 6 received. The polymers in these examples were all made with a catalyst composition according to the invention manufactured. The vapor phase bulk interpolymerization reactions, however, were each at one Ethylene / propylene ratio produced outside

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14th

of the range according to the invention. How to get from curve B in As can be seen from the drawing, the ethylene incorporated into each of the block copolymers was not very effective in achieving good impact resistance values. In fact, the incorporation of about twice the amount of ethylene is compared to conventionally produced block copolymers (curve A) necessary to produce products with the desired To maintain impact resistance.

Example 7, which was produced according to the invention, resulted a block copolymer with a significantly improved ratio of ethylene content to impact strength, (The point is indicated in the drawing.)

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Tabel

ο σ> ο ο

Example no. Cf. 1 Cf. 2 Versl. 3 Verel. A. Verse:!. 5 54 Beiscie "· 7 ■ L i Prepolymer product 23.8 93 T ί Temperature ⁰ C 54 54 63 54 54 150 54 2.8 ί Pressure - Kp / cm ~ 23.3 23.8 30.3 23.8 23.3 3.5 23.3 0.2 Al / Ti molar ratio 75 150 75 150 150 150 TIBA / MPT molar ratio 3.5 2.8 3.5 2.8 3.5 270 ' 2.8 3.0 ι Dwell time - hours ■ 2 hours -
271 20th I. Productivity 1000 kg / kg Ti 226 305 280 270 93/82 '333 2.0 j Vapor phase block polymer 93 2.8 0.103 i Temperature - ⁰ C 82 93 2.8 93 82 0.2 / 0.54 i
i Pressure atü 2.8 2.8 0.54 2.8 2.8 I.
j Ethylene / propylene 0.54 0.5 / 0.2 0.4 0.54 12.3 Block copolymer product 7.3 15th ! · *> Ethylene content -% by weight 6.2 6.5 15th 8.6 11.2 2.3 CD Block - wt% 11 18th 2.5 15th 31 0.212 Melt Flow - g / 10 min. 2.0 2.2 0.103 2.1 1.6 Notched impact strength 0.093 0.109 0.147 0.218 (mkg / cm)

+) These values were taken from

Anglo-Saxon unit of measurement ft.lb/in. using the factor

Examples 8 and 9

The polymer products from 2 continuous polymerization batches, which essentially correspond to that for the Examples 1-7 described procedure were prepared, but with the exception that 1.4 mol% of ethylene in the Feed stream of the prepolymer reactor was present in Example 9 and used triethylaluminum as cocatalyst were subjected to a detailed analysis. The results as well as the respective procedures

conditions are given in table 2.

As indicated in Table 2, ASTM standard test procedures were used to determine most of the properties of the polymer products applied.

The ratio of Mw / Mn was determined by liquid chromatography using o-dicorbenzene as a solvent certainly.

The content of Ti, Mg and Al was determined by atomic absorption analysis of the polymer ash dissolved in hydrochloric acid. The chlorine content was determined by colorimetric determination of the burned polymer sample using a ^{Parr? R>} Oxygen bomb.

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- yr- Example no. 1 e 2 8th 9 T a b e 1 catalyst FT-I FT-1 ΛIkylaIuminium TEA TEA Γ) Molar ratio Trialkylaluminxum / MPT 3.4 3.1 < Al / Ti molar ratio 150 150; Temperature of the first reactor, ° C approx. 54 approx. 54 ι 10 Pressure atü 23.5 24.5: Dwell time, hours 1.7 1.7 E / P molar ratio - 0.014 Productivity kg / gTi 353 437 2nd reactor temperature, C 80 80 Pressure atü 28.5 28.0 15th Dwell time, hours 2.0 2.0 E / P molar ratio 0.3 0.3 Additives: BUT - TpM 1200 1200 20th Iranox 1010 - pM 500 500 Calcium stearate - TpM 1000 1000 Hydrocalcite - TpM 1000 1000 Characteristics: 25th Total ethylene content -% by weight 4.2 6.7 Melt flow g / 10 min. (L) 0.8 2.1 Density g / cm ³ (2) 0.897 0.895 Mn 46.100 38,000 Mw 367,000 325,000 30th Mw / Mn 8.0 8.6 tensile strenght Yield strength kg / ^cm 300 24 7 Break kg / cm ² 216 211 Elongation at break -% (3) 516 485 35 Flexural modulus kg / cm χ 10 10.9 8.16 HDT + at 4.62 at ° C ⁽⁵⁾ 81 80

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Continued table

Polymer impurities crystalline melting point, ⁰ C hardness (Rockwell) (6) LTB ⁺⁺ - ⁰ C (7) Izod impact strength (8) mkg / cm

Ash - TpM Mg - TpM Ti- TpM
Cl - TPM Al - TPM

Example 8 Example 9 ^: 168 162 51.5 38, A - 12.8 - 20, A 0.233 0.29 A 395 350 37 33 3 2 98 95 255 19A

(1) ASTM D1238, Bed. L.

(2) ASTM D15O5

(3) ASTM D638 (A) ASTM D79O

(5) ASTM D6A8

(6) ASTM D.

(7) ASTM D7A6

(8) ASTM D256

+ = Bending temperature under load

++ = low temperature brittleness

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Claims (17)

Propylene-ethylene block copolymers, characterized through the following properties: A melt flow range between about 0.1 and 10 g / 10 min a ratio of weight average molecular weight to number average molecular weight (Mw / Mn) about 6.5, a proportion of polymerized ethylene of at least about 1.0, a titanium content not higher than about 3 ppm, a magnesium content not higher than about AO ppm, a chlorine content no greater than about 100 ppm and a total ash content no greater than about AOO ppm. 2. Block polymer according to claim 1, characterized in that it is produced by a process having the following stages has been: (A) Preparation of a preformed propylene polymer in finely divided form, with the preformed polymer residue contains on active catalyst and by polymerizing propylene in the presence of a catalyst composition which contains the following components: a) an aluminum trialkyl compound or an aluminum trialkyl compound which is at least partially has been subjected to complex formation with an electron donor compound and b) titanium tri- or tetrahalide on a magnesium dihalide support , or a complex of a titanium tri- or tetraholagenide with an electron donor compound on a magnesium dihalide support; (B) introducing the preformed polymer into at least one continuous, stirred reaction zone; 130065/0600 (C) Introducing ethylene and propylene monomers into the reaction zone in a molar ratio of ethylene Propylene from about 0.15 to about 0.3 and (D) polymerizing the ethylene and propylene monomers in the vapor phase in the reaction zone onto the preformed Propylene prepolymer. 3. Block copolymer according to claim 1, characterized in that the preformed propylene polymer is in a polymerization zone under sufficient pressure to keep the propylene in the liquid phase is. 4. Block copolymer according to claim 1 to 3, characterized ,. that the preformed propylene polymer is a propylene homopolymer. 5. block copolymer according to claim 1 to 3, characterized in that that the preformed propylene polymer is a disordered ethylene-propylene copolymer. 6. Block copolymer according to claim 1 to 5, characterized in that that as an aluminum trialkyi compound has been used which has 1 to 8 carbon atoms in contains the alkyl group, in particular triisobutyl aluminum or triethyl aluminum. 7. block copolymer according to claim 1 to 6, characterized in that that as an electron donor compound for component a) of the catalyst composition is an ester of a Carboxylic acid or a diamine has been used. 8. Block copolymer according to claim 7, characterized in that the electron donor is an ester of an aromatic Acid, particularly methyl p-toluate, has been used. 130065/0600 9. Block copolymer according to claim 1 to 8, characterized in that a molar ratio between the trialkylaluminum compound and the electron donor between 1 and 100, preferably 2 and 5, has been used. 10. Block copolymer according to claim 1 to 9, characterized in that the aluminum trialkyl compound has been reacted with the electron donor for less than one hour before the polymerization. 11. Block copolymer according to claim 1 to 10, characterized in that that titanium trichloride or titanium tetrachloride has been used as the titanium trihalide or tetrahalide. 12. Block copolymer according to claim 1 to 11, characterized that magnesium di-chloride has been used as the magnesium dinalogenide. 13. Block copolymer according to claim 1 to 12, characterized in that that the electron donor compound for component b} is a polyamine or an ester of an oxygen-containing one inorganic or organic acid has been used. 14. Bloch copolymer according to claim 13, characterized in that an ester is used as an electron donor compound aromatic carboxylic acid, particularly ethyl benzoate, has been used. 15. Bloch copolymer according to claim 1 to 14, characterized in that a molar ratio in component b) between magnesium and electron donor of at least 1, preferably between 2 and 10, is used has been. 16. Block copolymer according to claim 1 to 15, characterized characterized in that a titanium content (calculated as titanium metal) between 0.1 and 20 wt .-%, preferably between 1 and 3 wt .-%, in the supported catalyst 130065/0600 component b) has been applied. 17. Block copolymer according to claim 1 to 16, characterized in that that the catalyst components a) and b) of the reaction zone in a molar ratio of aluminum to titanium from 1 to 10,000, preferably between 10 and 200, have been added. 130065/0600