DE2024765A1 - Process for the polymerization of olefin monomers - Google Patents

Description

PATENT LAWYERS ZQ 2 S / b >>

dr. W. Schalk dipl.-ing. P.Wirth dipl.-ing. G. Dannekbi. c DR.V. SCHMIED-KOWARZIK DR. P. WE! N HOLD DR. D.GUDEL

6 FRANKFURT AM MAIN

OK. EfCHENMfIMEII «TRASSE 39

SK / ch.

Union Carbide Corporation

270 Park Avenue

Hew York, Ν.Ϊ. 10 01? / UNITED STATES Process for the polymerization of olefin monomers

The present invention relates to a process for the polymerization of one or more olefin monomers by means of catalyst systems which contain diarene chromium compounds applied to a support.

009849/1878

It is known that diarene "(bis->arene)"> metallv <irbinduneen -tin Ka.uuly ..- ι-gates act for the polymerization of olefins. However, the catalytic effectiveness of some of these compounds is garing. US Patents 3,123,571 and 3,157,712 describe processes in which the effectiveness of these catalysts is improved by using the compounds on a carrier, such as, for example, silica, alumina or silica clay.

Were these Diarenohrom-V .rbinuun ^ .- n uj Ethylen-Polymeris-itionskatalysatoren used, uo resulted uich '«'. -Il ^ r-j Problems. The catalysts showed a good effectiveness, apraehyn but not on hydrogen, which is generally used to regulate the Melt index of the Oltffinpolymerieate is used.

Said slide chromium compounds are very good olexin polyacrylate cationic catalysts, attempts have been made to improve their response to them To improve hydrogen so that the melt index of the olefin polymers could be regulated with the aid of hydrogen.

It has now been found that in a process for the polymerization of Olefins using supported diarene chromium compounds as catalysts, the response of the catalyst to the Regulation of the molecular weight of the polymer used water. Substance could be improved »by adding cyclopentadiene to the diarene chromium compound applied to a carrier. This will not only the exposure of the catalyst to this agent for regulating '

009949/1878.

BAD QRlasstNAL

-J-

Development of the melt index a improved, but the supply of cyclopentadiene also causes a change in the molecular properties of the polymerizate produced in this way * '

You modified according to the invention with traces of cyclopentadiene on Diarene chromium compounds applied to a carrier show better behavior compared to the hydrogen used to regulate the melt index, and in addition the molecular structure of the polymers thus obtained improved.

You as Olefin-Polymeriaationskatalyeatßran for the inventive Process .suitable organocetallic compounds are irene chromium compounds of the following structuredXi

Cr

In this formula, B stands for water stiff, η for an integer from 1 to 6 »R ⁸ for an alkyl group with 1 to about 6 carbon atoms _s nftr a gnzQ number from 0 to ^{3- and a + η 1} for 6 Examples of such compounds are Dibeaaolchroia _f Ditoluolohro * _t di-o-xylene chromium, 'li-p-acylolchroiBj Dicumolctoom, Diaeeltyleaciiroa, Bi "> (n-propylTbenisol) ™ chromium, di- (I _t -3f5 * 8' triet) -'Cro "_> Di- (I ₍ 3-diethyl-4-hexylbenzene) ohrOMt di- (i-t3 ^ dipentylben" ol) -hero "t di- (1,4-dihexylbenzol) chromium, di · (I, 3 »5-t ^ ihexylbeneol) -chroM, Di« «/ f2-iiotliiyltatyl) -1!> Eiizol7« »ete © ate ο

■ 0098A9 / 1818 ■ "'■

Examples of olefin monomers which can be polymerized according to the invention are monoolefins, such as ethylene and other carbon atoms with 3 Ms © fewa -10 carbon atoms, such as propylene, butene-1® phenyl-1, 3-methylbutene * 1, hexene-1 , 4-methylpentene-1, 3-ethylbutene-1 ₉ heptene-1 _t Oofen »1 ₉ decene-1 ₉ -4,4-dimethylpentene» 1, 4 »4" diethylhexene-t »3» 4 ™ I> ira9thylh @ x © a "1 _s 4-Butyl 1-octene, 5-ethyl-i-decene, 3,3" Diaethylbut © a ° 1 and others These compounds can be polymerized either as one or in combination with one another. The monoolefins can can also be polymerized with a © i © r ra @ hr © rea diolefins to form crosslinkable interpolymers. Examples of suitable diolefins are Btateäienj 1 ^ -ΈΒπ & άί @ η ₉ Bicycle pentadiene, ethylidene norbornene and the like «Polyethylene is the preferred Hoaopolymerisat. The preferred ©! ! Inteipolyinerisate Tbest @ fe @ n aas a gröeseren amount (ie, * ^ 50 percent, .- $ ") ethylene« nd a smaller amount (ie ^. 50 wt .- ^ C) a © of several other ₉ üfeliyiea inter poly meriaie E1; I (isri © "-Pi ^> © pylene" and ethylene-butene interpolymerizates which have at least 80% by weight of ethyl and up to 20% by weight of propylene are preferred. Bmt © a contain »Bi @ polymers are solid at a temperature of 25 °

The ketalyeators according to the invention are produced ₉ . First, the selected large surface area adsorbs the compound either through Aisofptisa aaa @ ia®a Lö8une? 0iiitt © l or through Basgfafesgtoaieliasug (Sttfeliüie ^ öBg) isa. called © inen töemiigsnlttelo © Bf sleia fes ^ ei? e the suitable carrier ³ fte ils läs, iP © a (Ste © a ° Ife ⁱ i!; Q3, ^ OG'S © s? offi

are silica, alumina, thore earth, zirconia and comparable inorganic oxides as well as mixtures of these oxides. The preferred carrier is a silica-alumina mixture. In order for the catalysts to be effective, the surface of the carrier must be large enough that a sufficient amount of the Diarenchroraverbinching adsorbed on it and sufficient contact between the catalyst and the reactive monomer is ensured. In general, should as a carrier for the catalyst inorganic oxides with an upper

2
area of about 50 to about 1000 m per gram can be used; however, the particle size of these carriers is not / particularly critical.

The catalyst support is preferably completely dried before it is brought into contact with the Diarenchrom connection. This drying is usually done by removing the carrier prior to use is heated with an inert gas. The drying of the carrier or its activation can be carried out at practically any temperature up to take place at about its sintering temperature and is carried out as long as until the adsorbed water is removed; however, drying is allowed not be continued long enough that all chemically bound water is also removed. In two ways, one leaves during the drying flow an inert gas through the carrier to remove it of the water to facilitate. Drying temperatures of about 200 ° to 900 ° are within a short period of about 6 hours generally sufficient if a well-dried inert gas is used and the temperature must not rise so high that the chemically bound hydroxyl groups removed from the surface of the support will. A particularly suitable carrier is the silica

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Alumina G-966 (W.R. Grace and Co.), which has a surface area of approximately 500 m / g and a pore diameter of 50 to 70 Å.

Once the diarene chromium compound has been deposited on the support, a modifying amount of cyclopentadiene is added. The amount of cyclopentadiene added is not very critical and can be between traces and about Ί5 mol, preferably between about 0.004 and about 12 Hol and in particular between about 0.04 ^and about 4 mol per mole of diarene chromium. The cyclopentadiene is preferably added to the diarene chromium compound in a solvent for the two compounds with sufficient agitation in an inert atmosphere to facilitate the desired modification of the diarene chromium compound.

After producing the invention,! applied to a carrier and modified catalyst systems, the polymerization is carried out by subjecting an olefin monomer charge in the virtually absence of moisture, air and other catalyst poisons with a catalytic amount of modified with cyclopentadiene and on one Slide chromium applied to the carrier at the initiation of the polymerization Brings suitable temperatures and bridges in contact. If desired, an inert one can be used to facilitate handling of the mixture organic solvent ala diluent in the reaction sintering are given.

00984971878

The polymerization takes place at temperatures of about} 0 ° or less up to about 200 ° or more »the polymerization temperature depends on strong mass of the work pressure, the bridge of the other monomers, the chosen catalyst and its consistency. Seibatverstünd-

The temperature is also determined by the melt index desired for the polymer, since the polymerization temperature regulates the molecular weight of the polymer and the melt index is a measure of the molecular weight. Preferably bei'Auf "is schlämmungs- or - worked löeungsbildenden" method with temperatures between 100 ° and 200 °, as described in more detail below, is in · ^"w ¥ Teilchenbildunga out at temperatures of about 30 ° to about 100 °, and in". this method desired temperature control * the molecular weight of the polymers au affect in various ways, and the phase au bestlmmen _v in the produced the polymers. As with most katalytiechen systems, the application performs higher temperatures sur formation of polymers having lower average molecular weight and If the polymer ionization process according to the invention is carried out at higher temperatures, polymers with a melt index of 100 to 1000 or more can be produced. Polymers with such a high melt index can be treated as wax, but still have a high density.

Any pressure that initiates polymer leation of the monomer feed is suitable for the method according to the invention. The reaction can i.e. at negative pressure using an inert gas as a diluent

009849/1878

voltage medium up to an overpressure of about? ü OOO atti been leading; a pressure between atmospheric pressure is preferred and about 70 atii, especially between 1.4 and 56 atU

A large number of inert organic solvents can be used in the process according to the invention. The solvents must be inert towards the monomer or monomers, the catalyst and the olefin polymer to be produced and must be stable under the chosen reaction temperature and pressure. However, you do not need to act as a solvent for the polymer produced. Examples of suitable inert organic solvents are the saturated aliphatic hydrocarbons; like hexane; Heptane, pen tasi ₉ isooctane, purified kerosene and the like; the saturated cycloaliphatic hydrocarbons, such as cyclohexane, cyclopentane, dimethylcyclopentene, methyloyclohexane and the like; the aromatic hydrocarbons; such as benzene, toluene, xylene and the like; as well as the chlorinated coal water such as chlorobenzene, tetrachlorethylene, dichlorobenzene Particular preference is given to cyclohexane pentane? Hexane

If the polymerization is to be carried out under such conditions that a high concentration of solids is achieved in the, the solvent must be used
Reaction operation to be fluid »If SoB ₀ to eiaox ³ fsmper & iur is being worked, which is lower than the LdsiMigsteuperatur eat Pelyaeipisaiboo in the solvent, eo that's! Erfahr®» in wesenfelisfesüa ola lhaf · = schläasBsuBgs «· @ pionaer © n @ n @ -Verfshr © a _o toi i © H ia ©

009849/1878

Polymer is precipitated from the liquid reaction medium and wherein the modified with cyclopentadiene and applied to a support Arenohrome catalyst in finely divided form in the medium is suspended.

Such a Aufschlämraungssystem depends of course on the during de.r Polymerization solvent used and the solution temperature of the polymer to be prepared from. With such "particle-forming" The process is therefore expediently carried out at a temperature which is lower than the normal solution temperature of the polymer in the chosen solvent. For example, polyethylene has a solution temperature of around 90 ° in cyclohexane, while its solution temperature in pentane is around 110. It is for these "particle" polymerization systems characteristic that a high content of polymer solids is achieved even at low temperatures can, if it is stirred in such a way that sufficient mixing of the monomer with the polymerizing mass is ensured. Although the Polymerization rate is slightly lower at low temperatures may be, the monomer appears to be more soluble in the solvent to be »so that there is a tendency towards low polymerization rates and / or low polymer yields are compensated for again will*

Another hallmark of the slurry process is that the Monomers also play a significant role in the solid parts of the slurry Seems to possess solubility, so that - as long as stirred and the

0098 4 9/1878

Polymerization temperatures are maintained - a wide range of sizes the / obtained polymorizate can be obtained in the slurry. It has been shown that with the help of the slurry method a Polymerieationssystem can be obtained, takes up to more than 50 wt .- $ consists of solids if sufficient vortex conditions are maintained and constant agitation is used throughout the process. Particularly preferred is a slurry process that results in a System with a solids content of 30 to 40 wt .- ^ polymer leads.

A high polymer solids content in the solution can also be achieved if one works at temperatures which are above the solution temperature of the polymer in the chosen solvent. at In this embodiment, the temperature must be so high that the solvent can dissolve at least 25 to 30 wt .- ^ of the polymer. On the other hand, however, the temperature must be set so low that neither the polymer produced nor the selected diarene chromium catalyst are destroyed by heat. The various solvents generally have temperatures between about 100 ° and about 200 °, preferably between about 120 ° and about 170 °, as optimal proven to carry out such a solution polymerization. However, the polymer to be produced also has a considerable influence for the optimal temperature. For example, the ethylene-propylene copolymers produced by this process are soluble in many organic solvents at low temperatures, and the use of such temperatures is therefore possible according to the invention, whether

009849/1878

these temperatures are probably not desirable for the optimal production of ethylene co-polymers or other copolymers are.

Solvents are the strongest and most difficult source of catalyst poisoning. Furthermore, in the previously known solution polymerization processes in which catalysts were used, the common metals contained "the use of large amounts of solvent, i.e. a weight ratio of solvent to polymer of about 20-1", considered necessary. These large amounts of solvent naturally also increased the risk of catalyst poisoning. In the method according to the invention can the ratio of solvent to polymer isi or even less which increases the productivity and effectiveness of the catalyst of the system is kept at a very high level.

If the solvent is the main reaction medium, it must are conveniently kept practically free of water and other catalyst poisons, indea it before its use in the

again Process / distilled or otherwise purifies. One treatment with an adsorbent such as silica or clays with large surface, molecular sieves or the like., Removes impurities that impair the polymerization rate or could poison the catalyst during the reaction.

009849/187 8

The polymerization can, however, optionally also be carried out without the use of a solvent. For example, the liquid monomer itself, serving as the reaction medium, can either be made up of commercially available liquefied monomers, as is the case in the production of ethylene-propylene mixed polymers using liquefied Frozenlen _β or dureii Arfoeiten under such pressure that the moraaLerwais © gasförail ^ e monomers becomes liquid, or when used with 'an eioh f here

Will be another advantage of erfiadungsgenäss © "¥ © rfahreas is seen in the fact" that the catalyst and the polymer formed solution gefcielten in the Lösungsmitteliüediuii _o Ba dl © Polymerisatsuspensioa avoided "to di behaves © surprisingly like a viscous Fliefistoff" nd läset look AITT © Pumping using the method known for such fluid material © '

Another advantage of a sate in the diluent is «that with high heat8. Temperatur@n sabers» © 15

The viscosity of the solution is increased by high temperatures

also cause a more rapid progression of the temperature, due to the large * temperature difference between the cooling water and the effective derivation of the heat, a regulation ^{1 of} the iteletalergewi ^ hteeυ temperatures and in general the lildmag v @ a Poljae ^ iaatQsi alt molecular weight.

Precipitation or filtration processes can be used to separate the polymer from the solvent medium, or the polymer / solvent mass is concentrated by flash evaporation or other solvent removal methods and then processed on high shear mills. Such high shear mills are commercially available; Due to the low solvent content of the solution to be treated, other devices, such as ventilated extruders, calender roll mills, planetary rotors, Banbury mills or the like, can also be used to isolate the polymer. By the term "high shear mill" is meant a mill which has two parallel rollers with intermeshing turns and the term "high shear ¹ *" refers to the conditions achieved with such mills or with sufficiently powered high power mixers for viscous materials.

High solids systems can handle that in a solvent suspended catalyst can be used if the required Conditions, namely stirring, pressure, temperature and the like., Are maintained and good contact of the monomer with the catalyst is guaranteed and when pressure and temperature lead to an initiation lead to the polymerization.

According to the invention, however, the fixed catalyst bed can also be used in one gaseous system swirled and with a gaseous Olefinbeachikkung are brought into contact) is unnecessary in this embodiment

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. I ₄ -. ■

the use of liquid solvents and problems related to Separation of the solvent or poisoning of the catalyst will be avoided.

The amount or concentration of the modified with cyclopentadiene and Oierenchrois-Katal / sators attached to a carrier iut for last The method according to the invention is not decisive5 due to the amount of catalyst essentially only affects the reaction rate and the yield achieved · So can with about 1 to 25,000 parts by weight Catalyst worked per million parts by weight of olefin feed will. Most economical is a catalyst concentration of about 5 to 100 parts per million. It is obvious that the The lower the degree of contamination, the lower the catalyst concentration of the reaction system 1st «. The proportion by weight of the carrier in the catalyst is generally 10 to 100 times the weight of the slide chromium compound. However, this ratio is not critical and can vary widely.

During the polymerization, care must be taken to ensure that neither moisture nor air (oxygen) can get into the reaction zone and poison the catalyst.

The molecular weight of the polymer can be regulated by the Polymerization is carried out in the presence of hydrogen, which appears to act as a chain transfer agent. The hydrogen can the polymer! sationmisohung in amounts of about 0.001 to about 10 mol per mole of olefin can be added * In most polymerizations

009849/187 8

a narrow molecular weight distribution can be achieved by about 0.01 to about 0.5 moles of hydrogen per mole of olefin used "In other words, the preferred" hydrogen concentration is between about 0.001 and about 5 M0I-9 &, based on the total heat odor.

As already stated, the slide chromium compounds are effective catalysts for olefin polymerization. If they are not modified by adding cyclopentadiene, theirs is theirs Flexibility is limited. A'thylenpolymerleate, which were produced at polymerization temperatures below 100 ° with a catalyst that had not been modified according to the invention »show ta general a very low Sehmelzindex, which is below 0.11 - the lowest value that can still be used for trading. Hydrogen starred when using these non-modified catalysts of the melt index, there was no noticeable improvement. It was also found that the polymers thus obtained

(FließverhMltniej "flow ratio") Risate a high flow value, which is a sign of a broad molecular weight distribution is, and the molecular analysis of the Products gave a high level of unsaturation.

In contrast, as the following examples show, the modification with cyclopentadiene % u resulted in a considerable improvement in the response to hydrogen, so that the melt index of the product could be controlled relatively easily. It was also found that the polymers were much more saturated and showed a narrower molecular weight distribution, d.fc. low ©

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• - 16 -

Tile values. From this it can be concluded that by adding Cyclopentadiene made a significant and unexpected change in that catalytic behavior of applied to supports Diarenchromverbindungen is achieved.

The properties of the 'described in the examples below Polymers were determined using the following methods

Density - ASTM Method D-I505 Melt Index - ASTM Method D-1238 Melt Flow - ASTM Method D-1238 (at 190 °

and 31 kg / cm **

Fliseswert .- Melt flow (FlieUhabennia) Melt index.

Methyl and _r Ungeeättigtheits Analyeent was the optical density of the corresponding infrared bands is measured and used in the following equations?

(A 7.25i *>) (33.8) i CH ₃ - t ((il)

Trans Unsaturation - Vinyl Unsaturation -

* (mils /

pendant ( "pendant") methylene. . ", / _E -i * \ unsaturation -

In these equations, A stands for the optical density «defined as

/ i, where Io is the incident light and I is the emitted light » and t stands for the thickness of the film sample (in mil)

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Controls A through Q _Λ

There were 17 ethylene polymerizations (controls A to Q) with a applied to a support but not modified with cyclopentadiene Dicumolchrom catalyst carried out.

The catalyst was prepared by using a preactivated silica-alumina Carrier was added under an inert atmosphere to oxygen- and moisture-free hexane, whereupon for deposition Dicumolchrom was added to the support. The mix turned 15th Stirred for up to 30 minutes to maximize deposition · of the dicumolchromium compound on the support, and then the resulting system was stored in hexane under an argon atmosphere before use.

_ ■ been

By heating to 500- the carrier was activated /. About 0.40 to3 0.45 g of the carrier were used as the base material for the diuminol chromium catalyst used in each reaction. Unless otherwise stated, the reaction took place in each case at 91 to 93 ° in moisture and Oxygen-free hexane under solution conditions and under a total pressure of 21 atm.

The results of control experiments A to, which are summarized in Table I. E show the influence of hydrogen and certain reducing agents on the lard index - the measure of the molecular weight - of Äijhylenpolymerisate obtained.

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Table II summarizing the results of controls F through K, shows the influence of temperature in the absence of hydrogen the melt index of the ethylene polymers

From Table III, which lists controls L through Q, is the influence of temperature on the polymer structure can be seen j it reveals the type of polymer structure when using one that is applied to a carrier, but not modified Dicumolchrom Katalyaators is to be expected.

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Table I. Respondents

control • Reducing agent Art Hillimol A. Dicumolchrome,
mg - B. 43 Dietary
alusinium
ethoxide 0.26 O
O
co
00
■ r- C.
D. 22nd Triethyl
aluminum 0.25 9 / V878 22nd
43

Polymer properties

Melting-Schnelz- density, atii index flow g / ccm

no river 0.007

0.002

0.05 0.09

Ο, θ 1.45

1.57

12 21

0.947

VO I

0.944

Table II

control * Polymer properties Yield, ff / h Melt index Melt flow Density, ίτ / ccm F. Reaction temp., ⁰ C 113 no river 0.05 0.947 ο β. 71 164 no river 0.8 0.947 to H
I. 93 123
92 2.21
10.8 184 0.946
O »934 849/1 J 118
137 45 5.02 382 0.943 co K 150 - 69 33 0.952 «Ο 167

Table III
Polymer properties

Control of reaction conditions <& Methy l <& Viny l $> Trana yes attached methylene

O L. see control F traces 0.21 - 0.02 M. see control G 0.51 0.48 0.03 0.01 H see control Ξ 0.75 0.72 0.07 traces OO see control I. t, 3 0.80 0.16 0.04 OO P. see control J 0.89 0.63 0.04 traces ft see control K 0.61 0.66 0.05 0.02

Table I shows that a _t applied to a support, nichtaodifisierter catalyst "of the used at temperatures below 100 ° C and in the absence of hydrogen (Control A), a polymer with KF melt index (no flow) leads. By using a hydrogen pressure of 3.5 to 7 * tti (controls D and E), the melt index of the polymers was only 0.05 respectively. 0.09 increased. The use of organic aluminum reducing agents (controls B and C) did not result in a significant change in the tendon index of the polymer produced in this way.

Table I seigt that when using deposited on a support, but non-modifisiürtem Bicumolokroa only polymers received a Schnelasindex for the w @ it®r «fomrteitan® toau @ lnber © n if teaperfttwea v © a very alia- 100 ° (controls H to K) work is going on "

Furthermore, it was found that the applied to a carrier, not « modified dicumolchromium catalysts only deliver polymers with a usable melt index if they are

the cheap ones drive used turn | / Aufsohlätaeiangsverfaferea deliver no © good

Results.

9 8 4 9/1878

Examples 1 bla 9

Nine ethylene polymerizations were carried out using dicumolchrome supported on a support and modified with cyclopentadiene as the catalyst.The support was activated at 530 ° and the dicuraolchroa was applied to the support in the manner described for the controls * To modify the catalyst Then about 15 to 30 minutes after mixing the dicumol chromium with the moisture- and oxygen-free hexane-alumina-silica slurry under an argon atmosphere, cyclopentadiene added to the slurry.

The effectiveness of the old cyclopentadiene-modified dicumolchromium catalysts and the properties of the ethylene polymers produced with them are shown in Tables IV and V below.

Each of the ntun reactions was performed under suspension conditions in 500 com moisture- and oxygen-free hexane at a temperature of 92-93 ° and a total pressure generated by ethylene and hydrogen τοπ 21 atm. In example 5 the hydrogen pressure is 7 atmospheres and in the other examples it is 3.5 atmospheres. The catalyst used in Example 3 was made by adding 0.24 millimoles Triäthy! Aluminum further modified.

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Table IY catal.yaator components

Polymer properties

example Cyclopentadiene U) c
Mol 10 ³ Dicumolchrom (B) _Λ
Mol 10 ⁴ ή / Ά Yield,
*/H Melt index,
d «/ min Flow value 1 ecm 0.6 ecm 1.4 0.04 136 0.03 --- 2 0.0005 1.2 40 1.4 0.08 33 0.86 41 O 3 0.001 n / A 40 0.7 0.17 42 0.87 41 O
co 4th
5 0.001 1.2
1.2 20th 1.4
1.4 0.08
0.08 25th
50 0.79
6.6 42
49 849/1 6th
7th 0.001
0.001 6.0
12.0 40
40 1.4
1.4 0.40
0.80 20th
12th 2.4
2.2 37
33 878 θ 0.005
0.01 60.0 40
40 1.4 4.0 11 3.2 37 9 0.05 120 40 1.4 8.0 11 3.5 35 0.10 40

O CD CD ■ Ρ-CP

Density,
# / ccm Table V 7.9 - ίο methyl ίο vinyl %> Trans $ with respect to methylene I. 0.956 35 41 0.26 0.30 0.02 0.01 ro
VJl Product from
example 0.956 Polymer properties 56 41 0.41 0.07 0.05 0.02 I. 1 0.957 Melt-Melt-Flow
indez river worth 33 42 0.37 0.14 0.02 0.02 2 0.948 0.03 90 37 0.51 0.09 traces 0.02 5 0.943 0.86 115 33 0.83 0.03 0.05 0.01 4th —— 0.87 * 0.65 0.05 no 0 _D 01 5 0.79 6th 2.4 3.5

K) O lsi

Example 10

On the feiet described for the preparation of the Dioumolohroa catalysts, 35 ng of Dibensolohroa were deposited on 0.4 g of a heat-activated (530 °) silica-alumina support. After the deposition had ended, 0.001 cc »cyclopentadiene was added} the molar ratio γόη cyclopentadiene to chromium was 0 _f O7i1. The catalyst was used for the polymerization of ethylene in an autoclave equipped with a stirrer and containing 500 cob of anhydrous and oxygen-free hexane. The reaction took place at 92 ° under a hydrogen pressure of 3.5 atm and a total pressure from 21 atu. After 1 hour of polymerization, 40 e of an ethylene polymer were obtained with a solvency index of 0.8 dg / min * and a flow value of 43.

Example 11

The procedure of Example 10 was repeated, but instead von Dibensolohroa 39 ag Ditoluolchroa were used. After 1 hour 36 g of an ithylenpolyerisates were old with a Sohmelzindex of Of7 dg / min, and a flow value of 41 was obtained.

The reactions of Examples 10 and 11 were carried out under slurry conditions

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Claims (2)

Patent claims! 1i process for the polymerization of one or more olefin monomers bit of a catalytic amount of a diarene chromium compound applied to a support at a temperature and pressure sufficient to initiate the polymerization »characterized in, that win of the slide chromium compound applied to a carrier ^ before initiation of the polymerization, cyclopentadiene is added. 2. The method according to claim 1, characterized in that as Diarenchroa compound Diouaolchroa, Dibenzolchroa or Ditoluolchroa is used. 3 · The method according to claim 1 and 2, characterized in that « Cyclopentadiene as a modifier in an amount up to about 15 moles is used per mole of diarene chloride. m 4. Process according to claims 1 to 3, characterized in that ethylene is polyaerized as olefinic monomer. 5 × process for the preparation of an olefin polymerization catalyst by adsorption of a ^ Diarenchromverbindung on an inorganic Oxydträger with large ^ r surface under inert conditions, "characterized in that after deposition of the _t Diarenchrom- 0.09849 / 1878 compound uuf the carrier cyclopentadiene is added. 6 »The method according to claim 3, characterized in that dicumolchrom, dibenzolchrom or di toluenechrom is used as the diarene chromium compound. The patent attorney! 009849/1878 COPY