DE2332890A1 - CONTINUOUS PROCESS FOR THE MANUFACTURING OF ELASTOMERIC COPOLYMERISATES OF AETHYLENE WITH A HIGHER ALPHAOLEFIN - Google Patents

Description

Cologne, June 25th, 1973 Eg / Ax / Hz

Continuous process for the production of elastomeric copolymers of ethylene with a higher oC -olefin

The invention relates to an improved method of manufacture of elastomeric copolymers of ethylene with higher oc-olefins, especially the production of EPDM elastomers with a relatively wide molecular weight distribution with a very narrow distribution of the composition, i.e. the proportions of the components.

Numerous Ziegler (Pyp. The most common Ziegler catalysts are the vanadium and titanium halides, used alone or in combination can be used with a wide variety of organoaluminum compounds as reducing agents.

By using different combinations of these Ziegler catalyst systems, it is possible to regulate and adjust the molecular weight distribution, the gel content, the distribution of the monomer sequences and the amount of monomers in the respective EPDM elastomer, as well as many other properties of the polymers. In this context, there is a correlation known as "polydispersity" (Q) between the weight average molecular weight and the number average molecular weight. This relationship is expressed empirically as H ₁₁ ZS _n . As is known, Q can have a value up to about 20, which indicates a very wide molecular weight distribution within a given polymer sample.

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This property, together with the molecular weight and the composition of the polymer, has a direct influence the processability of the elastomer. However, until the time of the invention it was not known like EPDM elastomers can be produced with a certain combination of properties. This combination is an expanded molecular weight distribution and a narrow composition distribution.

It is known that certain Ziegler catalysts reactivate using a series of at least three reactors can be. The EPDM reaction is carried out in all three reactors by removing all of the catalyst added to the first reactor and a reactivator added to the following stages. A recently granted The patent that gives this teaching is US Pat. No. 3,629,212. This manufacturing process has the disadvantage that by the reactivator incurs increased costs and cleaning problems.

It has now been found that the molecular weight distribution of EPDM elastomers with a simultaneous narrowing of the distribution the composition, i.e. the proportions of the constituents, in a continuous process below Using a row consisting of two reactors can be expanded without using a reactivator. This is achieved by adding a solvent, the monomers, the catalyst and the organoaluminum compound to the first reactor as a cocatalyst at a temperature of -50 ° to 150 ° C and a pressure of 0 to 70 atmospheres, withdraws the polymer cement from the first reactor and the second reactor together with additional cocatalyst and feeds monomer or catalyst. The second reactor is at essentially the same temperature and held at the same pressure as the first reactor. The contents of the reactor are made using a cooled diluent used in the reactor insert

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QfBGUNAL IN

kept at a relatively constant temperature by means of

The EPDM elastomer obtained has a Q value of 2 to 8 The product is made using one by mixing VOCl with Ti (OR) ^ (where R is C 1 -C 4 alkyl) Catalyst component produced as a catalyst. As an organoaluminum compound that acts as a reducing agent is preferably an alkyl aluminum sesquihalide used.

The invention is described below in connection with the process scheme shown in the figure. The monomers, solvents, the catalyst and the cocatalyst are fed continuously to the stirred reactor 1 fed. The polymer cement is removed without killing or otherwise deactivating the catalyst components introduced directly from reactor 1 into reactor 2 by the breakdown within the reactor. The reactor 2 will be continuously supplied additional monomer and / or cocatalyst, catalyst and solvent. In none A reactivator is introduced into the reactors. The monomers are polymerized further in reactor 2.

The temperature in the reactors is made proportionate through the use of heat exchangers or other conventional means kept constant. Preferably, the temperature is increased by introducing a chilled diluent into maintain the reaction zone.

Following the polymerization in reactor 2, the polymer cement is discharged and catalyst deactivators are added, where the cement is "deactivated", the polymer is isolated and sent for finishing. After this Second reactor can be used conventional methods and deactivating agents used to the combined Deactivate catalyst components and unreacted

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ORIGINAL

Monomers, solvents and finished polymer from the Recover or isolate reaction mixture. As is common with all Ziegler-Natta polymerizations, all monomers, solvents and catalyst components completely dried and of dissolved moisture or other ingredients known to affect the activity of the catalyst system, freed. Feed tanks, lines and reactors can be removed by covering them with a dry inert gas, e.g. nitrogen, to be protected.

Any hydrogen can be supplied through separate lines Stage or with the solvent of the first stage or with the monomers in the subsequent stages for Adjustment of the molecular weight are supplied.

The EPM or EPDM elastomer produced in the process is an interpolymer of ethylene with one or more higher α-olefins with 3 to 3 carbon atoms, preferably Propylene (EPM). In addition, a non-conjugated acyclic or alicyclic diene can be added in order to introduce unsaturated units into the polymer (EPDM).

Monomers

The method according to the invention is suitable for homopolymerization of α-olefins, e.g. ethylene, propylene and Butene-1, however, the invention is mainly related to the production of elastomeric copolymers of ethylene with a C ^ -Cg-α-olefin and elastomeric terpolymers of Ethylene with one C, -Cg-α-olefin and one non-conjugated acyclic or alicyclic diolefin directed.

As representative examples of O, -Cg-α-olefins which are known as Monomers that can be used with ethylene for the production of copolymers or terpolymers are:

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A. Straight-chain acyclic α-olefins, e.g. propylene, Buteaia-1, pentene-1, hexene-1 and octene-1.

B. Branched acyclic α-olefins, b.B. 3-methylbutene-1, 4-ethylpentene-1 and 5 »5-dimethylhexene-1 ·

O, alicyclic, i.e. carbocyclic α-olefins, e.g. vinylcyclopentane, Allyl cyclopentane and vinyl cyclohexane.

As representative examples of non-conjugated diolefins, which can be used as third monomers in the terpolymer are:

A. Straight chain acyclic dienes, e.g. 1,4-hexadiene, 1,5-hexadiene and 1,6-octadiene.

B. Branched acyclic dienes, for example 5-methyl-1,4-hexadiene, 3-7-dimethyl-1,6-octadiene, 3 % 7-dimethyl-1,7-octadiene and the isoarerene mixtures of dihydromyrcene and dihydroocimes.

C. Alicyclic dienes with a ring, e.g. 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-cyclododecadiene, 4-vinylcyclohexane, i-Allyl - ^ - isopropylidenecyclohexane, 3-Allylcyclopenten, 4 — allylcyclohexene and i-isopropenyl-4— (4-butenyl) cyclohexane.

D. Alicyclic dienes with multiple fused and bridged Rings, e.g. tetrahydroinden, methyltetrahydroind, Dicyclopentadiene, bicyclo (2,2,1) hepta-2,5-diene, 2-methylbicycloheptadiene, alkenyl, alkylidene, Cycloalkenyl and cycloalkylidene norbornenes, e.g. 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene norbornene, 5 "(4-gyclopentenyl) -2-norbornene and 5-Cyclob.exyliden-2-noΓboΓnen.

The suitable non-conjugated diolefins contain im generally 5 to 14 carbon atoms, and those containing them Terpolymers have mean values calculated from the viscosity

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OWQINAL INSPECTED

23:

Molecular weights from about 30,000 to 350,000, preferably about 100,000 to 250,000, determined in decalin at 135 ° C.

Structurally, the terpolymers according to the invention can for the various third non-conjugated diene monomers as random polymers with the following components being represented:

ι 'Χ

Higher α-olefin units

Ethylene units

t- ι Z

H-C-C-C-CH,

III t>

HHH 1,4-hexadiene units

H H

> H ₂

HC-CH

Higher a-01efin units

Ethylene units

■ ** ■

Higher α-olefin ethylene units units

H ₂ C

HC-CH

Tetrahydroinden units

H H I I

HC-CH ₂ -CH

H ₅ CC

NS,

5-ethylidene-2-norbornene units

Herein, x, j, and ζ are integers that generally range from 1 to 15.

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Solvents and dispersants

Suitable media for dissolving or dispersing the catalyst components and the fieaktionsprodukte and for Heat exchange can be selected from the general group of petroleum hydrocarbons and halogenated hydrocarbons to get voted. Straight-chain or branched saturated C ^ hydrocarbons or lower are preferred Hydrocarbons, however, saturated alicyclic or aromatic Cc-C ^ hydrocarbons can just as well be used. Halogenated hydrocarbons with 2 to 6 carbon atoms in the molecule are also suitable. Liquid propylene can also be used. As examples of representative solvents and dispersants that are also suitable for removing the heat of reaction, the following are to be mentioned: propylene, propane, butane, pentane, cyclopentane, Hexane, cyclohexane, methylcyclopentane, heptane, Methylcyclohexane, isooctane, benzene, toluene, mixed Xylenes, cumene, dichloroethane, trichloroethane, o-dichlorobenzene and tetrachlorethylene-perchlorethylene).

Main catalysts

For the purposes of the invention, transition metal compounds of metals of groups IVb, Vb and VIb of the periodic table are used as catalysts. Vanadium and titanium compounds are particularly advantageous. Vanadium compounds of the general formula VO ₂ X ₁ J., in which ζ has a value of 0 or 1 and t has a value of 2 to 4, are particularly preferred. X is independently selected from the group consisting of halogens having an atomic number of 17 or greater than 17, acetylacetonates, haloacetylacetonates, alkoxides, and haloalkoxides. Examples include VOCl ₅ , VCl ₄ , VO (OEt) ₃ , VO (AcAc) ₂ , VOCl ₂ (OBu), V (AcAc) ₅ and VOCl ₂ AcAc, in which (AcAc) is an acetylacetonate. VOCl, is preferred.

The titanium compounds that can be used in combination with vanadium compounds are general

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ORJQtNAL INSPECTEO

23 ?. ^; · 90

Formula Ti (OR) ^, in which H is an acyclic or alicyclic monovalent hydrocarbon radical with 1 to 12 carbon atoms is.

Particularly preferred of the usable catalysts are vanadyl trichloride (7001,), vanadium tetrachloride (VCl ^) and tetrabutyl titanate (Ti (OBu) ^), which in combination with VOCl, is used.

Oocatalysts

Suitable cocatalysts for the purposes of the invention are reducing organometallic compounds from the groups Ha, lib and lilac, in particular organoaluminum compounds of the general formula AlH ¹ X ¹ , in which R ^{1 is} a monovalent hydrocarbon ^{radical, namely a 0} I ^-0 ^ p "alkyl radical, - Alkylaryl, arylalkyl or cycloalkyl, m is a number from 1 to 3 »X * is a halogen with an order number of 17 or more than 17 (Cl, Br and I) and the sum of m and η ■ 3. Various mixtures of Cocatalysts can be used.

Examples of suitable cocatalysts are Al (Bt) ,, Al (isoBu) ,, Et ₂ AlCl, EtAlCl ₂ and Et, Al ₂ Cl.

Reaction conditions

1 x temperature ; The polymerization is preferably carried out at temperatures ranging from -50 ° to 150 ⁰ C, 0 ° to 100 ⁰ C, in particular 10 ° to 70 ° C.

2. Pressure : The pressure at which the polymerization is carried out depends on the reaction temperature and the rate of polymerization, but the pressure is kept so high in each case that it corresponds to the vapor pressure of the solvent and of the reactants as a whole. In the particularly preferred temperature range, the pressure that is required, including the reaction

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to keep participants in the liquid phase, at around 4.2 to 21 atm.

3 · Concentration of the monomers : Depending on whether an elastomeric EPM copolymer or an elastomeric EPDM terpolymers is to be produced, the monomers of the first stage and the subsequent stage are fed in a preferred molar ratio. For a typical EPDM elastomer, the monomers are introduced into all stages, for example, in the following amounts: ethylene 2 to 15 parts by weight, preferably 3 to 10 parts by weight per 100 parts by weight of solvent; Propylene 4 to 30 parts by weight, preferably 6 to 20 parts by weight per 100 parts by weight of solvent, and 5-ethylidene-2-norbornene 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight per 100 parts by weight of solvent.

M- · Catalyst concentration : The transition metal catalyst, for example TOCIx, is, if necessary, diluted with a solvent, fed to the first reactor in such a way that its concentration in the total solvent is 0.01 to 5 »0 mmol, preferably 0.05 to 0.5» mol / l.

The organoaluminum compound used as cocatalyst, which can also be diluted beforehand with the solvent, is at the same time the first stage in such Amount supplied that the transition metal catalyst is brought to maximum activity. The molar ratio of Organoaluminum compound to transition metal catalyst is generally in the range of 1.0 to 20 moles of organoaluminum compound per mole of transition metal compound

The second reactor can contain the organoaluminum compound in the same amount or in an amount greater than that are fed to the first reactor.

Hydrogen can be used in an amount to adjust the molecular weight and the molecular weight distribution at all stages

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from 1.0 to 10,000 parts per million parts of ethylene added will.

The above description shows that, according to the invention, the monomers, cocatalysts and hydrogen in any combination can be introduced into the second stage. It is possible to use the transition metal catalyst to be fed only to the first stage.

The reaction zones can also be arranged in another way in order to avoid the use of two series-connected Reactors achieved good results. A horizontal Partition wall can be installed, which divides the reactor into two separate zones for the polymerization. At a In such an arrangement, separate feeds are provided for each reaction zone. The solvent, the monomers, the catalysts and cocatalyst are each zone in the same order as two separate reactors fed.

With both methods it is possible to change the addition of different components of the insert. Depending on the composition of the polymer desired in each case, additional ethylene, higher α-olefin or non-conjugated diene can be fed to the second reactor or the second zone alone or in a specific combination. It is also possible to introduce all of the monomers used in reactor 1 into reactor 2

As a further variant, a different organoaluminum compound than in reactor 1 could be used in reactor 2. For example, if diethylaluminum chloride is used as cocatalyst in the reactor 1, ethylaluminum sesquichloride could be introduced into the reactor. 2 Interesting effects on the molecular weight distribution were found with this procedure .

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The invention is further illustrated by the following examples explained #

example 1

Two with cooling jackets (not shown) provided on The cascading reactors shown in the figure were used for those described below Experiments used · At the steady state, reactor 1 had a volume of 5 »68 1 and at the overflow the reactor 2 has a volume of 5 »68 1. The temperature in the reactors 1 and 2 by precooling the reactor insert maintained by, controlled by a sensitive! temperature controller, cooling water through the jacket was circulated. The catalyst component dissolved in the solvent was precisely metered into the reactor using a pump.

The catalyst and cocatalyst were introduced into the first reactor in the following amounts:

1) VOCl ₅ -Ti (0-butyl) ₄ : 1.5 g / hour.

2) Diethylaluminum chloride (Et ₂ AlOl): 6.3 g / hour. The molar ratio of VOOl to Ti (O-butyl) ^ was 2: 1. The catalyst was diluted with hexane. The catalyst components were introduced into the second reactor in the following amounts:

1) Et ₂ AlCl: 3.15 g / hour.

2) VOCl ₅ -Ti (O-Bu) ^: 0.75 g / hour.

The remaining feedstocks were in the amounts given in Table I below in reactor 1 and / or introduced.

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Reactor use 2332890 Table I. Reactor 1 Use, R / hour 40,000 Reactor 2 n-hexane 900 - Ethylene 2700 - Propylene 5-ethylidene-2-norbornene (ENB) 54.0 - -

The temperature of both reactors was kept at 32G. The ethylene-propylene-ENB polymer formed in the first stage was introduced as cement into the second stage, where the additional catalysts were added and further polymerization took place.

The residence time in each of the two reactors was 5 minutes. An ethylene-propylene-ENB terpolymer was used in this experiment obtained with a relatively wide distribution of composition and molecular weight. The efficiency of the catalyst was relatively low compared to the tests in which the used Monomers were distributed to the reactor stages.

Example 2

Using the apparatus described in Example 1 and following the same general procedure, the Introduced monomers and catalyst components into the reactors in the amounts specified in Table II Experiment, the monomers used were divided between reactors 1 and 2, while the catalyst and the cocatalyst total of the reactor 1 was fed. Hexane was introduced into both reactors as a solvent. The temperature of the reactors was about 32 ° C and the pressure was maintained at about 4.2 atmospheres.

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Reactor 1 reactor 2 620 5,000 15.OCX) 1 21% 1.50 1.50 4.50 4.50 0.09 0.09 - 0.0075 - 0.0075 - 0.0315 6.6 6.6

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Table II Shared use of monomers

Use (g / 1OO g hexane)
Hexane, g / hour
Ethylene
Propylene

VOCl,

Ti (0-butyl) ₄
Et ₂ AlCl
Dwell time, minutes

Catalyst efficiency (g polymer / g VOCl ₃ ;

Propylene conversion

A mixture of the following composition was produced with the polymer formed:

Polymer 100 parts

FEF carbon black 70 "

SRF foot 30 "

Naphthenic Oil (Flexon 886) 100 "stearic acid 1

ZnO 5

Sulfur 0.85

TMTDS (tetramethylthiuram disulfide) 0.5 TDEDL (80%) 0.5

DPTTS 0.5

MBT (mercaptobenzothiazole) 0.5

After vulcanization for 20 minutes at 160 ^° C., the polymer mixture had the following properties:

Tensile strength 121 kg / cm ²

Elongation 660%

Module at 300% elongation 44 kg / cm ²

Shore A hardness 46

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ο ο -? "ο η

The original polymer had a L'ooney viscosity ML-260 (1 + 8) of 42, an ethylene content of 60.5 wt .- #, a number average molecular weight (Mn) of 70.0 χ 10 "'and an intrinsic viscosity (IV) of 3.0 ..

Example 3

Using the same apparatus as in Example 1 and following the same general procedure, the monomers and catalyst components were added to the reactors in the amounts shown in Table II. In these? All, the monomers fed in were divided between reactors 1 and 2, while the catalyst and the cocatalyst were introduced exclusively into reactor 1,
However, ethylaluminum sesquichloride was added to reactor 2 as a second cocatalyst.

Table IHA
Shared Feeding the monomers and using a

second cocatalyst mission C. g / 100 R. Hexane)
Hexane, g / hour Ethylene Propylene EIIB VOCl ₃ Ti (OBu) ^ Et ₂ AlCl Et ₃ Al ₂ Cl ₅ Re aktortempe temperature Pressure Dwell time, minutes

Efficiency of the catalytic converter,

g polymer / g VOCl ₃ 613

Propylenuia rate 21% % By weight ethylene 59.5

"" ENB -2.9

Mooney Viakosity ML-260 (1 + 8) 30

Intrinsic viscosity 2.7

Mn χ 10-5 309883/1345 70.0

Reactor 1 Reactor 2 I5.OOO 15-000 1.50 1.50 4.50 4.50 0.09 0.09 0.0075 - 0.0075 0.0315 - - 0.0107 32 ⁰ C 32 ° C 4.2 atm 4.2 atm 6.6 6.6

A mixture of the composition mentioned in Example 2 was prepared with the polymer formed. The mixture was ^{vulcanized at 160 °} C. for 20 minutes. The VuI-kanisat had the following properties:

Table IIIB: Properties

Tensile strength 117 kg / cm ²

Elongation 680%

Module at 300% elongation 41 kg / approx. ²

Shore A hardness 44

The polymers prepared according to Examples 2 and 3 clearly show better rubber properties than the polymer prepared in the manner described in Example 4 for comparison. Also would result Elution fraction studies of these polymers a very narrow distribution in terms of composition. This was confirmed by infrared analysis and intrinsic viscosity determinations (in decalin) confirmed

Example 4

In the manner described in Example 2, but with the introduction of all monomers and the catalyst (including the cocatalyst) was only in the first reactor a polymer prepared with the properties given in Table IV.

Table IV: Comparative test Mooney viscosity ML-260 (1 + 8) 29 ethylene 57.7% by weight

ENB 3.5% by weight

Intrinsic viscosity 2.1

Mn χ 10 ^-5 57.0

Properties of the vulcanized polymer mixture (as in example 2)

Tensile strength 91.4 kg / cm ² elongation 590%

Module at 300% elongation 34 kg / cm ²

Shore A hardness 44

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The experiments described in the following examples were carried out to the when using two cascaded Possible variations in the addition of the monomers, the catalyst and / or the cocatalyst are possible to illustrate in the manner described above

A continuous flow multi-stage reactor system as described in Example 1 was used in all experiments described below use ethylene, propylene and hydrogen as chain transfer agents (if used) could be added as GaBe to both reactors will. All starting materials were purified in the usual way to avoid poisons for Ziegler catalysts remove. The catalyst (vanadium compound) and the cocatalyst (aluminum alkyl) were separated into the Introduced reactor in which the active catalyst is in

öitu formed. The reactor pressure was 1.03 to 1.1 kg / cm In some trials, all of the catalyst, all of the cocatalyst, and the hexane were used as the solvent introduced into the first reactor.

The product emerging from reactor 2 was passed into a separator, where the unconverted gases were blown off and the polymer cement was collected. The solvent was later stripped from this solution removed with steam. The isolated polymer was dried by pressing.

In Examples 8 and 9, one consisting of two reactors was used System with a 3.8 liter reactor and a 11.36 liter autoclave connected in series was used. The reactors were operated at 5.3 kg / cm. There was no gas phase, but the mode of operation was im rest the same as described above

The conditions and results of the in Examples 5 to The experiments described in Table 9 are listed in Table V.

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Examples 5 »6 and 7

These three experiments illustrate the influence of working in two reactor stages on the molecular weight distribution. Changes in molecular weight distribution are difficult to achieve in a single reactor, however the results given below clearly show how easily it is possible to change the molecular weight distribution in a multi-stage reactor system

In the case of Example 5, the first reactor stage produced 85 # polymer in which the ratio of the viscometrically determined molecular weight to the number average molecular weight (My / ^ l was 2.2. This indicates a polymer which has a narrow molecular weight distribution and is difficult to process.

In Example 6, the ratio KyM _n was therefore increased to 3.5 and the molecular weight distribution was expanded in that only 50% of the polymer was formed in the first stage. In Example 7, hydrogen was introduced into the first stage as a transfer agent (Hp / VOCl, »3.0 mol / mol). This resulted in a further expansion of the molecular weight distribution and a polymer that was easier to process and had a B ^ / H ^ value of 4.0.

The catalyst used in these experiments

Al ₀ Et _x used. The results are given in Table V.

Examples 8 and 9

These experiments were carried out in the 3 »8 l reactor and in the downstream 11.35 l reactor, using 2VOC1, /! Ti (OBu) u -AlEt2Cl as catalyst and a terpolymer of ethylene, propylene and 5-ethylidene -2-norbornene (ENB) was produced.

In Example 8, the 3.8 liter reactor was used alone and ENB supplied in an amount of 0.21 kg / 100 kg hexane · The

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The efficiency of the catalyst was 665 · In Example 9 the product emerging from the 3.8 1 Beaktor was the 11.35 1-Heaktor together with additional monomers and Solvent supplied. A polymer with the same ethylene content and the same Mooney viscosity as in Example 8 was formed, however the catalyst efficiency was increased from 665 to 956. The results are given in Table V.

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CmXkH INSPECT «?

Tabel

co

eat OO 00

P- cn

at
game Temp,
1 ⁰ Ci
2 Stay
Time,
Minutes 2 Old/
Moles /
Mole Fresh food,
Parts by weight / 100
Share hexane Ethylene 2 Weight / Ie η Effect
degree of cat.
Parts by weight Polymer All in all Polym.
Together
settlement V
K Mooney
Visc.
at 5 1 12th Cat. 1 1.0 Propi 2 risat / part by weight
from the 388 Weight -i « C ₂ 100 ⁰ C 6th 29 33 12th 11 8th 0.008 1.2 1.1 1 3.8 V \ J \ jX ~ r
1 335 47 2.2 7th 11 27 10 11 8th 0.009 0.75 1.1 1.8 5.0 330 382 44 3.5 34. 8th 11 26th 11 0 8th 0.009 0.75 0 0.93 4.5 169 - 43 4.0 58 9 26.5 - 13.5 28 6.5 D.OO75 3.2 2.0 0.93 0 187 956 53 40 26.5 32 13.5 6.5 0.008 3.2 9.5 10.0 665 53 60 (127 ⁰ C) JO, 0 - 59 (127 ⁰ C)

VD I

CO INJ CO CO O

Claims (9)

Claims A continuous process for the preparation of elastomeric copolymer! Sowed of ethylene with a higher Cz ^ ⁰ n "ot-olefin, and optionally additionally with an acyclic or alicycIisehen nonconjugated diolefin, characterized in that one behind the other on two Rührwerksreaktoren, a) Ethylene, a higher C ^ -C ^ Qa-olefin and optionally additionally the acyclic or alicyclic nonconjugated diolefin, a Ziegler-Natta catalyst, which consists of at least one transition metal component and a cocatalyst in the form of an organoaluminum compound of the formula R AlX, in R is a monovalent hydrocarbon radical from the group consisting of G ^ -G ^ g- alkyl radicals, alkylaryl radicals, arylalkyl radicals and cycloalkyl radicals, m is a number from 1 to 3, X is a halogen atom with an atomic number of 17 or more than 17 and the sum of m and η = 3, into the first reactor, b) a portion of the monomers in the first reactor at a temperature in the range of -50 ° to 150 ⁰ C and a pressure of 0 to 70 atmospheres to form a polymer cement polymerizes c) the polymer cement from the first reactor into one connected in series with the first reactor second reactor leads, d) ethylene, the higher C ^ -C -Q-α-olefin, additional acyclic or alicyclic non-conjugated diolefin and / or the transition metal catalyst and / or the cocatalyst in the form of the organoaluminum compound of the formula R AlX, in which R, m, X and η are those mentioned above Have meanings in the second reactor, e) the monomers are polymerized further under essentially the same conditions as in the first reactor, 309883/1345 f) the contents of the second reactor emptied and the Polyraerization reaction of the emptied contents ended and g) the copolymer is isolated and worked up. 2. The method according to claim 1, characterized in that additional ethylene, the higher C, -C _lo -a-olefin and acyclic or alicyclic non-conjugated diolefin are added to the second reactor. j5. Method according to claim 1 or 2, characterized in that that the monomer use of ethylene, propylene and one there is a small proportion of a non-conjugated acyclic or alicyclic diolefin. 4. The method according to claim 1 to 3, characterized in that that 5-ethylidene-2-norbornene is used as the non-conjugated diolefin. 5. The method according to claim 1 to 4, characterized in that that as Qrganoaluminium cocatalyst in the first reactor diethylaluminum chloride and in the second reactor Ethyl aluminum sesquichlorld is given. 6. The method according to claim 1 to 5, characterized in that VOCl is used as the transition rivet component. 7. The method according to claim 1 to 5 *, characterized in that that as a transition metal component VOCl, in combination with Ti (0-butyl) 2j. is used. 8. The method according to claim 1 to 7 *, characterized in that that additional transition metal catalyst component is added to the second reactor, 9. The method according to claim 1 to 8, characterized in that it is carried out in the presence of a solvent, with additional solvent being added to the second reactor. S09883 / 1345 Blank page