DE1520337A1 - Vulcanizable copolymers of di- or polyalkenylbenzenes, ethylene and alpha-olefins and processes for their preparation - Google Patents

Description

PATENT LAWYERS 1 R? Π Τ * 3

DR.-ING. BY KREISLER DR.-3NO. SCHDNWALD DR.-ING. TH. MEYER DR. FUES

COLOGNE 1, DEICHMANNHAUS Patent attorney "

Dr.-fng. by Kreisler Dr.-Ing. Sdiönwald

Or.-Tns.Tb.Moyer Dr.Fues DipI.-Chem.AiokvonXrehUr

KpUkm. Corolo Mn Of.-Jng. KIdd

Cologne, 27.II.1968 Ke / IK

Company Monteeatini Societa Generale per ^l'f lndustria Mineraria e Chimica, 1-2 Largo G. Donegani, Milan / Italy

Vulcanizable copolymers of di- or polyalkenylbenzenes, ethylene and α-olefins and processes for their manufacture

The invention relates to essentially linear, amorphous high molecular weight copolymers of di- or polyalkenylbenzenes which are completely soluble in boiling aliphatic solvents with ethylene and one or more higher α-olefins, using special catalysts The copolymers contain monomer units in every macromolecule, those of all the monomers used originate, and after vulcanizing with sulfur * containing mixtures elastomers with good mechanical properties,

The production of copolymers from olefinic monomers and alkenylbenzenes - is known. For example was the production of copolymers from styrene and divinylbenzene described, but the products obtained here were due to their poor properties for not suitable for practical use; because they were brittle, insoluble and practically infusible materials represent.

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U & U8 UiTiarfagen iArt. 7 Paragraph 1 Paragraph 2 Wr. 3 sentence 3 of the amendment ». * &. '.'

U.S. Patent 2,989,515 describes the preparation of copolymers of one or more olefinic monomers with dialkenylbenzenes, in particular with divinylbenzene, with the aid of essentially heterogeneous catalysts, preferably composed of a titanium compound and an aluminum trialkyl or a lithium aluminum tetra .alkyl. Also in this In this case, only partially soluble and thus crosslinked products are obtained, which become tough and hard. The possibility, by copolymerization of ethylene with one or more aliphatic oc-olefins and di- or polyalkenylbenzenes to manufacture linear, amorphous, soluble products after vulcanizing with sulfur-containing mixtures Elastomers yielding good mechanical properties has not yet been described.

It has now surprisingly been found that products with the properties mentioned can be obtained if the copolymerization is homogeneous or substantially homogeneous catalysts are used, which are produced by the conversion of vanadium compounds and halogen-containing aluminum or organic beryllium compounds can be obtained. To achieve a narrower molecular weight distribution, vanadium compounds are preferably used the manufacture of the catalyst used in the hydrocarbons used as solvents for the copolymerization are soluble.

Preferred vanadium compounds are the halides and oxyhalides, for example VCl ₂ ^ VOCl, or VBr ₂₁ , and those compounds in which at least one valence of the metal is saturated by a heteroatom attached to an organic group, in particular oxygen or nitrogen, such as vanadium triacetylacetonate and tri -

9 0 9 8 2 7/1 Λ 3 7

BADORTOlNAL

benzoylacetonate, vanadyl diacetylacetonate, halogen acetylacetonates, trial alcoholates and halogen alcoholates, tetrahydrafuranates, Etherates, aminates, pyridinates and quinolates of vanadium tri- or tetrachloride and of vanadyl trichloride. It is also possible to use vanadium compounds which are present in hydrocarbons to produce the catalyst are insoluble, preferably organic salts such as vanadium triacetate, tribenzoate and tristearate.

The organoaluminium or beryllium containing halogens Compounds that work together with the above vanadium compounds can be used to prepare the catalyst are preferably from the following Compounds selected: dialkyl aluminum monohalides, Monoalkylaluminum dihalides, aluminum alkylsesquihalides, Complexes of said organoaluminum compounds with preferably weak Lewis bases and alkylberyllium halides,

Examples of organometallic compounds of the type mentioned above are: diethylaluminum monochloride, Diethyl aluminum monoiodide, diethyl aluminum monofluoride, Diisobutyl aluminum monochloride, monoethyl aluminum dichloride, Aluminum ethyl sesquichloride, di (cyclopentylmethyl) aluminum monochloride, Diphenyl aluminum monochloride, diisobutyl aluminum monochloride as a complex compound with anisole, beryllium methyl chloride.

Organometallic compounds in which the metal with main valences is not only attached to carbon and halogen atoms, but also to oxygen atoms,,. . . , are bound, dxe to an organic group / ^ eDunden, such as alkylaluminumalkyoxyhalides. Examples of such compounds are aluminum monochloro-monoethyl-monoethoxide, aluminum monochloromonopropyl monopropoxide and ethoxide.

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The catalyst systems obtained in this way are homogeneous or essentially homogeneous. You are in the Hydrocarbons that can be used as solvents in the copolymerization, for example finely dispersed in aliphatic, aromatic or cycloaliphatic hydrocarbons or mixtures thereof or colloidally dispersed.

The process for producing the copolymers can be carried out at temperatures in the range between -80 ° and + 125 ° C. To achieve high Copolymerausbeuten per unit weight of the catalyst, it is practical, both the catalyst preparation, as well as carry out the copolymerization at temperatures between 0 ° and -8o ° C, preferably between -10 ° and -50 ⁰ C,.

When working under these conditions, the activity of the catalysts is higher than that of the same, catalyst systems produced at higher temperatures. Furthermore, when the low temperatures mentioned are used in the course of catalyst production, the activity of the catalysts remains practically unchanged over time.

When using catalysts made from vanadium triacetylacetonate, Vanadyl trialkoxides or haloalkoxides and alkyl aluminum halides at temperatures between 0 ° and + 125 ° C, it is useful to achieve high copolymer yields in the presence of certain Complexing agent to work. Suitable complexing agents are ethers, thipethers, tertiary amines, trisubstituted ones Phosphines which contain at least one branched alkyl radical or one aromatic ring.

Ethers of the general formula RYR ¹ , in which Y is oxygen or sulfur and R and R ^! a linear or branched alkyl radical with

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BATH

1 to 14 carbon atoms or an aromatic nucleus with 6 to 14 carbon atoms and one of the radicals R and R ^{1 is} a branched alkyl radical or an aromatic nucleus; as well as tertiary amines of the general formula

in which R, R ¹ and R ″ are alkyl radicals with 1 to 14 carbon atoms or aromatic nuclei with 6 to 14 carbon atoms and at least one of these radicals is an aromatic nucleus, or tertiary phosphines of the general formula

in which R, R ¹ and R ^{11 are} alkyl radicals with 1 to 14 carbon atoms or aromatic nuclei with 6 to 14 carbon atoms and at least one of these radicals is an aromatic nucleus.

The amount of the complexing agent is preferably 0.05 to 1 mole per mole of alkyl aluminum halide. The activity of those used for the method according to the invention Catalysts can be modified by changing the molar ratio between the compounds used to produce the catalyst to be changed.

It has been found that, for example, when using diethylaluminum monohydrate (Al (C ₂ He) ₂ CI) and vanadium triacetylacetonate (VAc,) the best results are obtained when a molar ratio of Al (C ₂ H ₁₇ ) ^ Cl / VAc is between 2 and 20, preferably between 4 and 10, is used.

cycioaliphatic The process can be carried out in the presence of aliphatic / or aromatic hydrocarbons as solvents, both

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t b ^ U J J /

for example butane, pentane, heptane, cyclohexane, toluene, Xylene or mixtures thereof. Suitable solvents are halogenated hydrocarbons, such as chloroform, trir.lilorethylene, tetrachlorethylene, Chlorobensene brine or methylene chloride.

Particularly high copolymer yields per unit weight of the catalyst are obtained when the copolymerization in the absence of inert solvents using the monomers in the liquid state, i.e. in Presence of a solution of ethylene in the mixture to be polymerized and kept in the liquid state α-Olefins and the di ~ or polyalkenylbenzenes carried out will.

For obtaining copolymers of very uniform Composition it is twofold to work in such a way that the ratio between the concentrations of the monomers in the reacting liquid phase during the copolymerization is kept constant or at least as constant as possible * For this purpose: it may be advantageous to the copolymerization continuously with the continuous supply and discharge of a monomer mixture more constant Carry out composition and work with high space air velocities.

Di- or polyalkenylbenzenes are used for the process according to the invention preferably the 3 to 8 carbon atoms in each contain alkenyl radical bonded to the benzene ring. For example, diallylbenzenes, allylbutenyl-2-benzenes, Allylbutenyl-3-benzenes and allylhexenyl-5-benzenes * It was found that particularly advantageous results are achieved when di- or polyalkenylbenzenes can be used in which at least one double bond is a vinyl double bond.

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As olefins, which together with ethylene and the above mentioned di- or polyalkenylbenzenes are used, the aliphatic α-olefins of the general formula come R-CH = CHp in question, in which R is an alkyl radical with 1 to 6 C atoms is. Particularly good results are obtained when propylene and / or butene-1 are used. For example is made by the copolymerization of a mixture consisting of ethylene, propylene and / or butene-1 and p-diallylbenzene consists, according to the inventive method, a crude copolymer! sation product obtained in boiling n-heptane is completely soluble and in every macromolecule in random distribution units of the monomers ethylene, Propylene (and / or butene-1) and p-diallylbenzene contains-

By changing the composition of the monomer mixtures, it is possible to change the composition of the copolymers within continue to change boundaries.

If amorphous copolymers of dialkenyl or polyalkenyl benzenes with ethylene and propylene are desired, is to maintain an ethylene / propylene oil ratio of less than 1: 4 or at most 1: 4 in the reacting liquid phase. Under normal conditions in the gas phase this corresponds to an ethylene / propylene molar ratio of lsi. Molar ratios from 1: 200 to are suitable 1: 4 in the liquid phase. If butene-1 is used instead of propylene, the ratio between Ethylene and butene in the liquid phase are not more than 1:20. The composition of the corresponding gas phase is then a maximum of 1: 1.5 molar ratio under normal conditions in the liquid phase between 1: 1,000 and 1:20 are generally satisfactory. Under these Amorphous terpolymers containing less than about 75 mole percent ethylene are obtained under conditions. If those Values are exceeded, the copolymer exhibits the

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- 8 crystallinity of polyethylene.

The lower limit of the ethylene content is not decisive, however, the copolymers should be at least 5 mol # Contains ethylene. The α-olefin content in the amorphous Copolymers is preferably between a minimum of 5 mol. # And a maximum of 95

The alkenylbenzene content of the terpolymer is preferably between 0.1 and 20 mol .- #. This upper limit can be increased, but it is not expedient, in particular for economic reasons, to introduce more than 20 mol % of alkenylbenzene into the copolymer.

Each monomer unit derived from the polymerization of di- or polyalkenylbenzene still contains one or more free double bonds. This can be seen, for example, from the fact that in the case of copolymers obtained from di- or polyalkenylbenzenes in which the double bonds are vinyl double bonds, bands at 10 and 11 ax are found in the infrared spectrum, which can be attributed to the presence of vinyl residues.

The copolymers according to the invention have an essentially linear structure. They therefore do not contain or Branches are only so few that their properties, in particular their viscosity behavior, match the properties known linear copolymers, for example the linear ethylene-propylene copolymers, practically are identical.

The viscometrically determined molecular weight of the copolymers according to the invention is over 20,000 corresponding to an intrinsic viscosity of more than 0.5, determined in tetrahydronaphthalene at 135 ° C. or in toluene at JO ⁰ C (see G. Moraglio "La Chimica el ^! Indust.ria",

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41 , 10 (1959), 984-987). The intrinsic viscosity of the copolymers can be 0.5 and 10 or even higher values. For most practical purposes, however, copolymers with intrinsic viscosities between 1 and 5 are preferred.

The composition of the copolymers according to the invention can be described as practically homogeneous. A confirmation of the homogeneity of these copolymers is the ease with the application of the generally accepted processes for the vulcanization of unsaturated rubber, especially rubbers which are only slightly unsaturated, such as butyl rubber, vulcanized well Products are obtained. This is also evidence that the double bonds along the Chain are well spaced.

In contrast to the unvulcanized polymers, which are completely soluble in boiling n-heptane, the Vulcanizates obtained in this way are completely insoluble in organic solvents and become through some aromatic solvents slightly swollen. The uncured copolymers have properties that are common to all non-vulcanized elastomers, since their initial modulus of elasticity is low and their elongation at break is low is very high. The vulcanized products have a high reversible elastic elongation and - especially at Use of reinforcing fillers such as carbon black at the same time high tensile strength.

Because of their good mechanical properties, they can be advantageous as well as all other synthetic rubbers in the field of elastomers, in particular for the production of hoses, air hoses or elastic threads. As an extender or Plasticizers can be used in general petroleum oils. Paraffinic and naphtha are preferred

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BATH ORIGINAL

- ίο -

Thenische oils, however aromatic oils can also be used will.

example 1

The reaction vessel consists of a glass cylinder with a diameter of 5 * 5 cm and a capacity of 700 ml, which is provided with a stirrer and inlet and outlet pipes for the gases.

In the held at a constant temperature of -20 ⁰ C reaction vessel 200 ml of anhydrous n-heptane and 5 ml of p-diallyl benzene are given. A gaseous propylene-ethylene mixture in the molar ratio νοφ: 1 is introduced through the gas inlet pipe and in an amount of 200 Nl / hour. circulated.

The catalyst is preformed in a 100 ml flask at -20 ° C. under nitrogen by reacting 1 millimole of vanadium tetrachloride and 5 millimole of diethylaluminum monochloride in 30 ml of anhydrous n-heptane. The catalyst formed in this way is siphoned into the reactor by nitrogen pressure. The gas mixture is in an amount of 400 Nl / h. in and out. After 2 minutes, the reaction is terminated by adding 10 ml of methanol containing 0.1 g of phenyl-β-naphthylamine. The product is purified and separated off in the usual way. After drying in vacuo, 5 * 1 g of a solid product are obtained which, on X-ray examination, turns out to be amorphous, is completely soluble in boiling n-heptane and looks like an unvulcanized elastomer. Examination by infrared spectrography reveals the presence of vinyl double bonds (bands at 10 and 11 Ai) and of phenyl rings. The ethylene / propylene molar ratio is about 1: 1.

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- li -

100 parts by weight of the ethylene-propylene-diallylbenzene terpolymer are in a laboratory roller mixer with 0.5 parts of 2,2-methylene-bis (4-methyl-6-tert-butylphenol) mixed as an antioxidant, 5 parts of zinc oxide, 1.5 parts of sulfur and 1.5 parts of mercaptobenzothiazole. The mixture is vulcanized in a press for 30 minutes at 150 ° C. A vulcanized sheet with the following properties is obtained:

Tensile strength 30 kg / cm

Elongation at break 420 %

Module at 300 % elongation 14 kg / cm

Deformation residue after

the fraction 2 % Ä

Comparative experiment

The experiment described in Example 1 was carried out using one of 1 mmol of vanadium tetrachloride and 5 mmol Triethylaluminum prepared catalyst repeatedly. The polymerization conditions and the amounts used the monomers are the same as given in Example 1.

The reaction is terminated after 2 minutes by adding 10 ml of methanol containing 0.1 g of phenyl-β-naphthylamine will. The product is then separated and purified. After drying under reduced pressure 4g of a solid product obtained which is X-ray amorphous. Infrared analysis reveals the presence of vinyl double bonds (bands at 10 and 11 yu) and of phenyl residues. The ethylene / propylene molar ratio is about 1: 1.

100 parts by weight of the terpolymer are placed in a laboratory roller mixer with 0.5 ^ / 2 ^ methylene-bis (4-methyl-6-tert. butylphenol), 5 parts of zinc oxide, 1.5 parts of sulfur and 1.5 parts of mercaptobenzothiazole mixed.

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§AD OWQtNAL

The mixture is placed in a press for 50 minutes at 150 ° C vulcanized. A vulcanized sheet with the following properties is obtained:

Tensile strength 20 kg / cm

Elongation at break 400

500 % elongation 7 k

Deformation rest 4o %

Module at 300 % elongation 7 kg / cm

The exceptionally high value of the residual Pormutungsrest compared to the value of the vulcanized copolymer according to Example 1 (2 %) proves that the product, which is obtained with catalysts based on halogen-free organometallic φ see compounds, has very poor elastomeric properties.

Example 2

In the held at a constant temperature of -20 ⁰ C :, reaction vessel of Example 1 200 ml of anhydrous n-heptane and 2.5 ml p-diallyl benzene are given. A gaseous mixture of propylene and ethylene in a molar ratio of 4: 1 is introduced through the gas inlet tube and in an amount of 200 standard l / hour. circulated.

In a 100 ml flask at -20 ⁰ C the catalyst is prepared under nitrogen by 0.7 millimoles vanadium dintriacetylacetonat 'and 3.5 millimoles of diethylaluminum monochloride in J> 0 ml of anhydrous toluene are reacted. The catalyst thus formed is maintained for 5 minutes at -20 ⁰ C and then siphoned into the reactor under nitrogen pressure. The ethylene-propylene mixture is continuously in an amount of 400 Nl / hour. in and out.

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BATH ORIGINAL

The reaction is stopped 7 minutes after the start by addition of 20 ml of methanol, the 0.1 g of phenyl-ß-naphthylamine contains, canceled. The product is purified and separated off in the usual way. After drying in vacuo 5 * 5 S of a solid product are obtained, which turns out to be amorphous in the X-ray examination, is completely soluble in boiling n-heptane and is not like a vulcanized elastomer looks like.

Examination by infrared spectrography reveals the presence of vinyl double bonds (bands at 10 and 11 αϊ) and of phenyl rings. The ethylene / propylene molar ratio is about 1 »! .. The ethylene-propylene-diallylbenzene terpolymer wiifd with the same mixture and under the same conditions as in example 1 vulcanized. A vulcanized plate with the following characteristics is obtained:

Tensile strength 37 kg / cm

Elongation at break 460 %

Module at 300 # elongation l8 kg / cm

20 deformation rest according to

the fraction 12 %

example

In the held at a constant temperature of -20 ⁰ C: reaction vessel of Example 1 containing 200 ml of anhydrous n-heptane, is added 2.5 ml of p-Dlallylbenzol. A gaseous mixture of propylene and ethylene in a molar ratio of 2 ti is introduced through the Oaselnführungrohr and in an amount of 200 Nl / h. circulated.

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BATH

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In a room kept at -20 ⁰ C 100 ml flask, the catalyst is prepared by mixing under nitrogen for 0.5 and 2.5 millimoles of vanadium tetrachloride Mlllimol diisobutylaluminum monochloride in J50 nil of anhydrous n-heptane are reacted. The catalyst preformed in this way is siphoned into the reactor under nitrogen pressure. The gaseous ethylene-propylene mixture is in an amount of 400 Nl / h. fed and withdrawn. The reaction is stopped 4 minutes after it has started by adding 10 ml of methanol containing 0.1 g of phenyl-β-naphthylamine. The product is purified and isolated in a customary manner.

After drying in vacuo, 6 g of a solid product are obtained which, on X-ray examination, turns out to be amorphous, what a non-vulcanized elastomer looks like and is completely soluble in boiling n-heptane. Analysis by infrared spectrography reveals that vinyl double bonds (bands at 10 and 11 λΐ) and phenyl rings are present and that the ethylene / propylene molar ratio is about 1 to 1.

The ethylene-propylene-diallylbenzene terpolymer is prepared using the same mixture and among the the same conditions as in Example 1 vulcanized. A vulcanized plate with the following key figures will be obtain:

Tensile strength 57 kg / cm ²

Elongation at break 4j5O %

Module at 300 % elongation 18 kg / cm.

Example 4

In dme kept at a constant temperature of + 25 ° C; 200 ml of water are added to the reaction vessel from Example 1.

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SAD ORIGINAL

given free n-heptane and 2.5 ml p-diallylbenzene. A gaseous mixture of propylene and ethylene in a molar ratio of 2: 1 is fed through the gas inlet pipe introduced and in an amount of 200 Nl / h. circulated.

The catalyst is prepared in a 100 ml flask under nitrogen by reacting 2 millimoles of vanadium tetrachloride and 10 millimoles of diethylaluminum monochloride in J> 0 ml of anhydrous n-heptane. The catalyst formed in this way is siphoned into the reactor under nitrogen pressure. The ethylene-propylene mixture is continuously in an amount of 400 Nl-hrs. circulated. The reaction is interrupted 10 minutes after it has started by adding 10 ml of methanol containing 0.1 g of phenylβ-naphthylamine. The polymer is purified and separated off in the usual way. After drying in vacuo, 6.4 g of a solid product are obtained which on X-ray examination turns out to be amorphous, is completely soluble in boiling n-heptane and looks like an unvulcanized elastomer. Analysis by infrared spectrography reveals the presence of vinyl double bonds. The ethylene / propylene molar ratio is about 1: 1.

The Kthylen-Propylen-Diallylbenzol-Terpolymer is with the same mixture and vulcanized under the same conditions as in Example 1. A vulcanized plate with the following key figures is obtained:

Tensile strength 70 kg / cm

Elongation at break 380 %

ο Module at 300 % elongation 23 kg / cm

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- 16 Example 5

In that kept at a constant temperature of -20 ⁰ C. 200 ml of anhydrous n-heptane and 5 ml of p-diallylbenzene are added to the reaction vessel from Example 1. A propylene-ethylene mixture in a molar ratio of 2 t 1 is introduced through the gas inlet pipe and in an amount of 200 standard l / hour. circulated.

In a 100 ml flask at -20 ⁰ C the catalyst is prepared under nitrogen by 1 millimole of vanadium tetrachloride and 5 millimoles Berylliummethylchlorid in JO ml of anhydrous n-heptane are reacted. The catalyst formed in this way is siphoned into the reactor under nitrogen pressure. The gas mixture is in an amount of 400 Nl / h. fed and withdrawn. After a period of 5 minutes, the reaction is terminated by adding 10 ml of methanol containing 0.1 g of phenyl-β-naphthylamine. The product is purified and separated off in the usual way.

After drying in vacuo, 6.5 g of a solid product are obtained which, on X-ray examination, turns out to be amorphous, is completely soluble in boiling n-heptane and looks like an unvulcanized elastomer. Examination by infrared spectrography reveals the presence of vinyl groups (bands at and 11 yes) and an ethylene / propylene molar ratio of about 1: 1.

The terpolymer is vulcanized with the same mixture and under the same conditions as in Example 1. A vulcanized plate with the following characteristics is obtained
Tensile strength 37 kg / cm ²

Elongation at break 460 %

Module at 300 % elongation 13 kg / om,

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BAD ORiOlNAL

Example 6

In a bath maintained at a constant temperature of -20 ⁰ C reaction vessel 200 ml of anhydrous n-heptane and 5 ml of p-diallyl benzene are given. A mixture of propylene and ethylene in a mol ratio of 4: 1 is introduced through the gas inlet pipe and in an amount of 200 Nl / hour. circulated.

In a 100 ml flask at -20 ⁰ C the catalyst is prepared under nitrogen by 1.4 millimole of VCl, -Tetrahydrofuranat and ¹ J mmoles diethylaluminum monochloride are reacted in 30 ml of anhydrous toluene. "The thus formed catalyst 5 minutes held at -20 ⁰ C and then siphoned into the reactor under nitrogen pressure. The ethylene-propylene mixture is continuously fed in an amount of 200 Nl / hr., And drawn off.

The reaction is stopped 17 minutes after it has started by adding 20 ml of methanol, 0.1 g of phenyl-β-naphthylamine. contains, canceled. The product is purified and separated off in the usual way. After drying in vacuo 6 g of a solid product which, on X-ray examination, turns out to be amorphous, in boiling water are obtained n-heptane is completely soluble and looks like an unvulcanized elastomer. The investigation by infrared spectrography indicates the presence of vinyl groups (bands at 10 and 11 ai). The ethylene / propylene molar ratio is about 1: 1.

The terpolymer is vulcanized with the same mixture and under the same conditions as in Example 1. " A vulcanized plate with the following key figures is obtained »

Tensile strength 35 kg / cm ²

Elongation at break 470 %

Module at 300 % elongation 15 kg / cm ² ^

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Example 7

In the held at a constant temperature of -10 ⁰ C the reaction vessel of Example 1, 200 ml of anhydrous n-heptane and 5 ml of p-Allylbutenyl-3-benzene added. A mixture of ethylene and butene-1 in a molar ratio of 1: 3 is introduced through the gas inlet pipe and in an amount of 200 standard l / hour. circulated.

In a 100 ml flask at -10 ⁰ C the catalyst is prepared under nitrogen by 1 millimole of vanadium tetrachloride and 5 millimoles of diethylaluminum monochloride in 30 ml of anhydrous n-heptane are reacted. The catalyst formed in this way is siphoned into the reactor under nitrogen pressure. The ethylene-butene mixture is continuously fed in and withdrawn in an amount of 200 W hours. The reaction is terminated 9 minutes after it has started by adding 10 ml of methanol containing 0.1 g of phenyl-β-naphthylamine. The product is cleaned and isolated in the usual way. After drying in vacuo, 6 g of a solid product are obtained which, on X-ray examination, turns out to be amorphous, looks like an unvulcanized elastomer and is completely soluble in boiling n-heptane.

Analysis by infrared spectrography reveals the presence of trans double bonds (band at 10.36 Ai), of methyl groups (band at 7 * 25 ^) and of methylene bands between 13 and 14 λχ.

The product is made using the same mixture and under the same conditions as in Example 1 vulcanized. A vulcanized plate with the following characteristics is obtained:

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Tensile strength 32 kg / cm

Elongation at break 510 %

Module at 300 % elongation 13 kg / cm.

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Claims (1)

Cologne, 11/27/1968 Ke / IK Claims , 1.) High molecular, essentially linear, volcanic "■ -—- '■' sizable amorphous copolymers of ethylene, one or more aliphatic oc-olefins of the general Formula R-CH = CHp, in which R is an alkyl radical with 1 to 6 carbon atoms, in particular propylene and / or butene-1, and one or more di- or polyalkenylbenzenes having less than about 75 moles of ethylene. 2.) Copolymers according to claim 1 with di- or polyalkenylbenzenes having 3 to 8 carbon atoms on each alkenyl radical, in particular diallylbenzene, allyl-butenol-2-benzene, Allyl-butenyl-3-benzene or allyl-hexenyl-5-benzene. 3.) Copolymers according to claim 1 or 2 with 5 to 95 mol % of α-01efinen and 0.1 to 20 mol .- # di- or polyalkenylbenzenes. 4 «) copolymers of ethylene, propylene and diallylbenzene. 5.) Copolymers of ethylene, butene-1 and p-allylbutenyl-3-benzene. 6.) Vulcanized elastomers from the copolymers according to claim 1 to 5 » 9 09827 / U3 7 UiU'oi'lclQGi ι ί -> '' ί. 7 s * l alsj. 2 i.r. 1 Sat; ·: 3 das Änrlcriinsrnss. ν. Λ. - ■> 7.) Process for the production of products according to claim 1 to 6 by copolymerization of the monomers in the presence of catalysts produced by the reaction of a vanadium compound and an organometallic Compound of aluminum or beryllium have been obtained, and optionally vulcanization of the products thus obtained, characterized in that the monomer mixture in Presence of a homogeneous or substantially homogeneous catalyst, in its preparation as with an inorganic component a halogen-containing compound of aluminum or beryllium was used, polymerized. 8.) Process according to claim 7 *, characterized in that catalysts are used which are derived from hydrocarbons soluble vanadium compounds, especially vanadium halides and oxyhalides or vanadium compounds in which one of the metal valences is replaced by heteroatoms, in particular oxygen or nitrogen bonded to organic radicals is saturated, have been obtained. 9t) Method according to claims 7 and 8, which are marked » draws attention to the fact that catalysts are used which are made from organic compounds that are insoluble in hydrocarbons Vanadium salts, particularly vanadium tri-acetate, vanadium tribenzoate and vanadium tristearate, have been obtained are" 909827 / U37 BATH 10.) Process according to Claim 7 to 9, characterized in that the organometallic catalyst components are used Dialkyl aluminum monohalides, alkyl aluminum sesquihalides, monoalkyl aluminum dihalides, Corplexes of such organoaluminum compounds with preferably weak Lewis bases, Alkyl beryllium halides or alkyl aluminum alkoxy halides used. 11.) Process according to claim 7 to 10, characterized in that the polymerization is carried out at temperatures between -8o ° and + 125 ° C. 12.) The method of claim 7 to 11, characterized in that when using catalysts of aluminum organic compounds catalyst preparation and polymerization at temperatures between 0 ° and -8o ° C, preferably carried out between -10 ° and -50 ⁰ C. 13.) The method according to claim 7 to 12, characterized in that that the polymerization is carried out in the absence of inert solvents. 14.) The method according to claim 7 bie 12, characterized in that that the polymerization is carried out in the presence of inert solvents for the catalyst, In particular aliphatic, cyoloaliphatic or aromatic hydrocarbons or halogenating hydrocarbons. 909827/1437 BATH OFMQINAL 15) Method according to claim 7 to 14, characterized in that that for the preparation of propylene-containing copolymers with molar ratios between Ethylene and propylene in the liquid, reacting phase less than or at most equal to 1: 4 is working. l6.) Process according to claim 7 to 14, characterized in that one works for the preparation of butene-1 containing copolymers with molar ratios between ethylene and butene-1 in the liquid, reacting phase of less than or at most equal to 1:20. λ ORIGINAL BATHROOM 909827 / U37