DE3008833A1 - METHOD FOR COPOLYMERIZING AETHYLENE WITH POLYUNSATURED HYDROCARBONS - Google Patents

Description

Oasis 1215
12/10 / bs

AITIC S.ρ.Α., Palermo / Italy

Process for the copolymerization of ethylene with polyunsaturated Hydrocarbons

The present invention relates to an improved process for the production of copolymers in high yield, starting from τ Ethylene, either alone or in admixture with one or more α-olefins, and a compound which has two or more uness contains te olefinic bonds which may be conjugated; "The process uses a catalyst system which i) an organometallic compound of Group III of the Periodic Table of the Elements and

ii) a compound produced by the reaction of magnesium contains metal or manganese metal vapor with a titanium compound and a Haiogendonat or.

The products resulting from the copolymerization of ethylene alone with the polyunsaturated compound are in the form of crystalline polymers.

Various processes have been described for the preparation of crystalline copolymers derived from the polymerization of ethyls with a conjugated or non-conjugated polyolefin and in particular butadiene and ethylidene norbornene (cf. for example DE-OSes 25 34 493, 25 34 497 and 27 32 110, according to German patent applications P 25 34 493.8, P 25 34 497.2 and P 27 32 110.4).

These processes are based on the coordinated anionic cat; Vanadium-based analyzers which, although they lead to high polymerization yields, do not achieve such a degree of activity.

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above to the need to difficult cleanings of the copolymer to prevent from the transition metal residues, which damage the oxidation stability of the copolymer and which lead to an undesirable Color lead. · In DE-OS 27 Q3 604 (corresponding to the German patent application.? 27 05 604.0) a catalyst composition described, which is extremely active in the polymerization and copolymerization of mono-a-olefins and is produced is made by reacting an organometallic compound of Group III of the Periodic Table of the Elements with a composition made by

i) evaporation or sublimation of magnesium in vacuo and ii) condensation of this vapor into a condensed phase which contains a litantetrahalogsnide and a halogen donor.

This DE-OS also describes that the activity of the catalytic composition in the homopolymerization and copolymerization of α-olefins is extremely high when the amount of evaporated magnesium metal is such that there is an atomic ratio of Mg / Ti in the condensed phase of well over 0.5 and a compound is present therein which is suitable for increasing the halogen to the magnesium metal in excess to the atomic ratio Mg / Ti of 0.5 corresponding to the complex MgXg ^ IiX * (X = halogen). In this way, MgXg is further formed, which reacts with the stoichiometric complex to form a new and more active complex containing sitane. It has now been found that by appropriately modifying the magnesium evaporation conditions and choosing the reagents and reaction conditions, it becomes possible to copolymerize ethylene, either alone or in admixture with other α-olefins, with a compound having one or more unsaturated olefin bonds contains, with highly crystalline polymers being obtained when ethylene is used alone. In addition to magnesium, manganese can also be used to produce the catalyst composition.

The activity of the catalyst system described above is such that an amount of copolymer per g of liter is achieved which is equal to or greater than 50 kg. The catalyst composition is prepared by evaporating the magnesium or

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Manganese, either in its metallic state or in the form e ner their alloys and condensing the steam into a kali solution, produced by dissolving a titanium compound and a halogen compound in an inert diluent.

The metal (M) can be used in powder form or in the form of granules or lumps, and is preferably evaporated by sublimation under vacuum. In the case of magnesium vai the temperature "(* 10 2 Torr his") ated as puncture of the pressure from 266 to 133 x10 between about 650 and 300 ⁰ C.

Manganese requires more vigorous conditions, namely 800 to 1100 ^c for 133 x 10 "is ¹ to 133 ac ~ 10 ⁴ Pa (or 10" * ¹ to 10 ^"4 Torr).

If the operation is carried out at a higher temperature, the metal can be vaporized from its molten state even at atmospheric pressure. The solution into which the damj is condensed is stirred at low temperature. In Be contraction to the solvent used this may be from ⁰ C to a temperature in the range of -120 to O are generally kept from -80 ° to -20 ⁰ C. The use of an inert Ye thinning agent, selected from low-volatile hydrocarbon solvents with a low freezing point (e.g. n-heptane, n-octane, toluene, etc.) is not absolutely necessary, as the reaction also occurs in the titanium compound and the halogenated Verbi fertilization can be carried out in its pure state.

Titanium tetrachloride is a liquid titanium compound suitable for this purpose and the alkyl halides are suitable as halogenated compounds, a measured excess forming the reaction medium.

Examples of alkyl halides that can be used see si 1-chlorobutane, 1-chlorohexane, and 1-bromohexane, however, are secondary or tertiary alkyl halides and aryl or alkylaryl halides also reactive. Of the inorganic halides, ha The following have proven to be the most suitable: SnCl., GeCl. and POCl ,.

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Among the titanium compounds, in addition to the tetrachloride other halides can also be used effectively, including the trivalent halides, the alcoholoates, the halo alcohols " te, the chelates and all organometallic derivatives. In practice, any titanium compound can be used, with the difference between them lies only in the speed of reaction.

The M / Ti ratio which is to be achieved in order to produce extremely active catalyst compositions exceeds 0.5 and in particular> 4. The preferred value for this ratio is from 15 to 30 and a further excess of M (Mg or wn) offers no benefit. The amount of the halogen donor compound which is present in the reaction is adjusted depending on the amount of M, based on this in a ratio or in an amount of ^ 2 in the case of monohalogenated organic compounds and ^ 1 in the case of inorganic compounds that are capable of supplying more than one halogen atom per molecule. The reaction between the M vapor and the Ti compound and the halogenated compound already partially takes place at the above low temperature. To complete them, either longer (a few days) standing at room temperature or, preferably, heating for a few hours (1-5), depending on the selected temperature (50-180 ^° C.), is necessary. The reaction is faster when the halogen donor is inorganic.

The halogen donor is at that kept at a low temperature; solution is not absolutely necessary, in which the metal vapor is condensed. It can be added later, but before the solution is raised to a higher temperature to complete the reaction.

The fine suspension prepared above is usually used directly as a catalyst component for the polymerization which follows is used provided that there is no excess of any of the reagents or any reaction by-products essentially disruptive agents for the formation of the

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ORlGlWAU INSPECTED

Represent catalyst. Alternatively, this suspension can be filtered and the solid can be again in the dispersing agent considered to be the most expedient, generally the same in which the polymerization is carried out, suspend! will. The solid compound can also be dispersed on an inert solid carrier, for example from the respective Polymer to be made is made.

As mentioned, the other catalytic component consists of egg an organometallic compound of an element of group II of the periodic table of the elements.

Among these elements, aluminum is the most widely used because of its effectiveness and expediency.

Examples of compounds that are used are the Sri alkyl and triaryl aluminum compounds such as Al (C ₂ Hc) JjAlCi-G, Al (C ₆ H ₅ ) ₃ , the alkyl aluminum hydrides such as Al (H) UC ₃ H ₇ ) ₂ and d alkyl and aryl aluminum halides such as Al (C ₂ Hc) ₂ Cl and (]

The Irialky derivatives are preferred, but they are also very good effective in a mixture with the halogenated derivatives.

The molar ratio of the organometallic compounds to the tan compound should exceed 3 in order to achieve a maximum specifi see effectiveness.

As a practical matter, this ratio is kept very high, for example 100 to 500, in view of the fact that extremely small amounts of the titanium compound are used in the polymerisation. As mentioned, the copolymerization process according to the invention is based on the copolymerization of ethylene with a conjugated or non-conjugated polyol and the use of the above catalytic components in the presence of an inert diluent at a temperature of 40 "to 120 ⁰ C and a working pressure of about 1 to about 20 bar. O to 20 kg / cm ² ).

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In the case of batchwise expiry, the reagents are so in the Reactor "charged that the catalyst either in the presence of the mixture of the "two monomers is formed or thus in Contact comes.

In practice "there are two working methods, of which" both are effective are. In the first, the catalyst component containing the titanium is introduced last, while in the second, the Reaction between the catalyst components, which afterwards "resp. to be added successively to the monomer mixture is carried out separately. In the latter case there is a pre-contact time which - although not critical - should not be extended very long, especially if a high Al / Ti ratio " is used.

The aliphatic hydrocarbons are preferably considered to be inert Diluent used. However, the presence of a diluent during the polymerization step is not absolutely necessary as it is possible to work in the gaseous state by introducing the catalyst dispersed in a small amount of low-boiling solvent.

The monomers, for example, for the copolymerization process according to the invention are listed below. Refer to the above mentioned conditions refer to the general case and all types of ethylene copolymers can be used by applying the method of the invention on the basis of that detailed for the copolymers below given teaching are produced within the scope of the present invention. For the person skilled in the art, it follows from the invention Teaches the possibility of choosing the most appropriate working conditions based on the desired polymer.

The monomers are ethylene on the one hand and a cyclic or acyclic hydrocarbon, which has more than one contains unsaturated bond which may be conjugated, on the other hand.

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Prototypes for these classes of hydrocarbons preferred because of their reactivity and low cost
are, 1 _{f are} 3-butadiene and 5-ethylidene- (2,2, i) -dicyclohepta-2 en (ethylidene norbornene).

They have a polymerization reactivity that is lower is than that of ethylene, which is why it is in excess (50 times or more) over the amount of the same monomer that zui Achievement of the copolymer is required to be charged.

This excess is used up by recycling its solution

The practically useful ethylene comonomer present in the copolymer is just a few percent (less a 10 f)

The molecular weight of the copolymer can be controlled by introducing hydrogen in addition to varying the reaction conditions. The hergeste by the method according to the invention th copolymers have properties that vary with their composition. The ethylene-butadiene copolymers contain drowning unsaturated bonds, whereas ice and vinyl unsaturations Bonds are absent or practically absent, which is due to a 1,4-trans addition of the butadiene units will be shown. The ethylene-butadiene copolymers rich in ethylene are characterized by densities of 0.940 to 0.960,

Melting points of about 130 ⁰ C and a distribution of unsaturated _; th bonds, as indicated by the -O-IMR spectrum of the figure
(which refers to a copolymer with 12.3 mol- $ butadiene), in which three maxima or peaks can be seen, the
can be ascribed to the differently structured butadiene units along the polymer chain (peaks which are ascribed to the methylene groups in the butadiene at a = 32.6, b = 32.7 and
ο = 32.9 ppm). It should be noted that analog copolymers prepared according to the prior art only have two of these three peaks
show in the C ₁ ^ in IR spectrum. It is known that crystalline Po! α-olefins, such as polyethylene, isotactic polypropylene, isotactic polybutene, etc., have been commercially available for some time

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ORIGINAL INSPE CTED

These poly-a-olefins "consist either of homopolymers or of Copolymers with small amounts of a second oc-olefin to "certain solve technical problems.

The amount of the second olefin is usually so small that the crystallinity is not excessive compared to the homopolymer is decreased because some important mechanical characteristics such as modulus, tensile strength, etc. are required to have high crystallinity are bound.

In the case of copolymers of ethylene with butadiene, this enables compatibility of the units of the two types in the same crystal essentially results in crystalline polymers via the entire composition range from pure polyethylene to pure trans-polybutadiene. In this! "All there is therefore none Limitation in the case of copolymers of mono-a-olefins exists, in which an olefin must be contained in a very small amount in the copolymer in order to maintain crystallinity in a to maintain a high level. A particularly important advantage of the copolymers produced by the process according to the invention is associated with the fact that they contain unsaturated bonds (either in the main chain, as in the case of butadiene, or in the side groups, as in the case of ethylidene norbornene).

By means of these unsaturated bonds, the copolymer can be easily crosslinked (with sulfur or other reagents) in order to achieve the technical characteristics such as thermal resistance, impact strength or resistance to agents, which induce the formation of environmental stress cracks, can be further improved.

The unsaturated bonds also allow certain transformations, which on the other hand would be difficult or impossible, such as foaming or thermal foaming of film materials or plate materials.

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-H-

example 1

A catalytic component that contains titanium is in one horizontally arranged rotating glass bulb of 1 1 manufactured, in the center of which is an electrically by means of a Tungsten filament heated aluminum crucible is located.

240 ml of n-heptane and 0.2 ml of TiCl were brewed in the flask and 0.9 g of magnesium turnings were put in the crucible. The solution was cooled to -70 ⁰ C.

After applying a vacuum to the rotating device (133x10 "" or 10 Torr) the crucible was heated with sufficient intensity by applying an electrical voltage to the ends of the thread to make him red hot.

Evaporation of the Mg gave a brown suspension, to which 8.2 ml of n-butyl chloride (1-chlorobutane) was added upon termination of the Ya knurns was added by introducing nitrogen.

The suspension was heated three hours 80 ⁰ C using a reflux condenser.

Cp ₁ P olymeris at i on

A stainless steel autoclave with a capacity of 5 1 and equipped with a mechanical stirrer and controlled electric heater was placed under vacuum and a prepared solution consisting of; anhydrous n-heptane 2200 dI

Butadiene 200 g

Al (G ₂ H ₅ ) ₃ 1-5 mmol

was then introduced by suction.

The temperature DEB autoclave was controlled at 70 ⁰ C before hydrogen and ethylene with partial pressures of about 3.5 or about 4.5 bar (3.5 and 4.5 kg / cn) were fed.

10 ml of the heptane suspension prepared as described above

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^ * "" ^^ '"? ^ fe INSPECTED

Sion containing 0.075 mmol of titanium was added to the autoclave introduced into an ethylene tiberdruok using a 100 ml Steel bottle equipped with a loading valve and an emptying valve il.

50 ml of a heptane solution of 7.5 mmol of Al (C ₂ Hc) Cl ₂ were then added during the first 5 minutes of the reaction to the mixture which was already in the autoclave, using a piston pump.

An immediate absorption of ethylene is found and this was fed in continuously, so that the original pressure at a temperature of 70 ^° C. remained constant.

After 3 hours it was found that the ethylene was still with an intensity approximately equal to the original intensity was absorbed. However, the test was interrupted and the suspension contained in the Autoclave was removed and filtered.

388 g of a dry powder with an MFI 2.16 of 49.5, a content of butanediene units (mol) of 3.3 $ and a melting point (Tm), determined by thermal differential analysis, of 131 ^° C. were obtained. which had the appearance of a white solid, very similar to the appearance of polyethylene, was mixed with the following compounds (g per 100 g of polymer): zinc oxide 5

Stearic acid 1

2,2'-methylenebis (4-methyl-tert-butylphenol) (A.0.2246) 1

IT-0xydiethylbenzothiazole-2-sulfenamide (NOBS special) 1.5

Dibenzothiazyl disulfide (Vulkacit DM) 0.5

Sulfur '3.

The Gemisoh was heated in a press 30 minutes 180 ⁰ C to form a product with 40 $ NaOH residue extracted with boiling xylenes (the polymer as such was completely soluble).

An investigation was made "at 85 ⁰ C using the autoclave

Example 2

A subi

and the method "described in Example 1" was carried out.

In this case "the partial pressures of ethylene" or Hydrogen about 5 "or about 3" bar (5 "or 3 kg / om) and there were
Introduced 250 g of butadiene. .

All other amounts were the same as in Example 1.

After 3 hours of polymerization, 250 g of dry copolymers were obtained which had the following characteristics:
Butadiene units = 3.3 $ (mol), MI ¹ I ₀ ,, = 0.84, Mi ¹ I ₀ .. c / MFI « _1f -32.5, Tm = 129 ⁰ C, impact strength = 13.7 kg / cm ² .

When crosslinked, as described in Example 1, showed the obtained Product has an impact strength of 50.4 kg / cm.

Example 3

A polymerization test was carried out using the same equipment and method as in the previous examples using the following reagents:
n-Iieptan 1840 ml

Butadiene, 102 g

Al (C ₂ H ₅ ) ₃ 17.6 mmol

H ₂ . 3.5 kg / cm ²

Ethylene 5.0 «

Ti complex (see Example 1) 0.06 mmol.

The autoclave was used both during the introduction of the gas and during the polymerization, in the course of which it was consumed Ethylene was supplemented, kept at 85 ° C.

Compartment 4 hours the test was interrupted and the product became filtered off and dried, giving 285 g.

The analysis gave the following results: butadiene units = 1.5j6 (mol), ^mi 2.16 = 0.99 g / 10 min., ^ ₂ T, 6 = ² ^, 4, Tm (DSC) = 133 ^° C

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Example 4

A solution prepared from 400 ml of n-heptane and 40 ml of bioyclo- (2,2,1) -5-ethylidene-2-heptene (Ethylidene norbornene) was placed in a stainless steel autoclave of the type described in Example 1, but with a capacity of 2 l, sucked.

The autoclave ^{temperature was controlled to 85 °} C. and ethylene and hydrogen were then fed in at partial pressures of about 5 and about 3 bar (5 and 3 kg / cm).

The catalyst, which consisted of a heptane suspension of the product obtained by reacting 5 mmol of Al (iC ^ H ₉ J ₅ with 0.012 mmol of titanium in the form described in Example 1 for 60 minutes at room temperature, was then prepared using a steel bottle and an N ₂ overpressure introduced.

The test lasted 1 hour, during which time the ethylene consumed was replenished so that its partial pressure was kept constant. The solid product obtained by filtering the suspension and drying weighed 35 g. It had the following characteristics: 3.3 # ethylidene norbornene (weight), MFI ₂ ^ g = 3.4 g / 10 min., MFI _{21 6} = 33, J20 min. = 0.9633 g / cm ⁵ .

Example 5

A catalyst component containing titanium was prepared in the same way as described in Example 1, but starting from the following reagents:
1-chlorooctane 120 ml

TiCl ^ 0.088 ml

Manganese metal 1.5 g.

The solution was cooled to -50 ° and a vacuum of 133 × 10 * "* Pa (or 10""* Torr) was applied, whereupon the manganese was evaporated and condensed. A dark brown suspension was obtained, which was then 1 hour to 100 ⁰ C was heated.

The chemical analysis showed that the homogenized suspension contained 5.10 mmoles / 1 Ti, 186.2 mmoles / 1 Mh and 390.0 mmoles / 1 Cl.

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Copolymerization

It was a Copolymerisationstest of butadiene and ethylene ö

performed using the Von described in Example 1 "

tion. The solution fed into the reactor was rock

n-heptane 2200 ml

Butadiene 250 g

AlU-C ₄ Hg) ₃ 22.5 mmol.

After controlling the temperature to 85 ^° C., the autoclave was pressurized with about 3 "bar (3 kg / cm) hydrogen and about (5 kg / cm ² ) ethylene.

• z

15 cm of the suspension containing the titanium complex, which was prepared as described above, was then brought in. Moreover, it was three hours ethylene added to d pressure at the original value of about 10 bar to keep (10 kg / cm) be 85 ⁰ C, after which the test was stopped and filtered the Pr and domestic product was dried.

200 g of polymer were obtained with the following characteristics 1,4-trans-butadiene units 5.15 $ (mol), MFI _{2 16} = 0.05 g / 10 Tm (DSC) = 132 ^° C., [^] (in decalin at 105 °) = 'i, 75.

Example 6

A catalyst component containing titanium was prepared

exhibits in a device analogous to that of Example 1

n-0otan 300 ml

TiCl ₄ 0.187 ml

SnCl ₄ 8 ml

Mg metal 1.2 g.

The magnesium was at 665 χ 10 Pa (5 σ 10 Torr) vapor and condensed into the solution, the WUR maintained at about-50 ⁰ C

The suspension obtained was brought to room temperature. Uj

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The solution overlying the decanted pesticide was for 24 hours free of titanium, whereas the homogenized suspension is 6.32 mmol / 1 Ti, 187 mmol / 1 Mg, 207 mmol / l Sn and 863 mmol / 1 Cl contained.

Copolymerization

The test was performed in the besohriebenen in Example 1 "autoclave at 85 ⁰ C ml using the procedure and the same reagents as in Example 5, except that the catalyst component containing titanium, this time from 11,85 of the foregoing The polymer obtained weighed 180 g and had the following properties: MPI _{2 16} = 0.1 g / 10 min. T _m = 131 ^° C. (DSC), butadiene units = $ 3.34 (mol).

In summary, the invention relates to the copolymerization of ethylene in high yields with polyunsaturated hydrocarbons using a catalyst system which is an organometallic "Compound of a metal of the third group of the Periodic Table of the Elements and a compound that contains is obtained by reacting metallic Mg or Mn with a Ti compound and a halogen donor.

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Claims (26)

Dr. F. Zumstein Sr. - Pr "g- ~% S9aicErifi - DrI-R: Kpenigsberger Dipl.-Phys. R. Holzbauer - DiprL-.fng. F. kuttg £ eis <9fT - Or. F. Zurnstein jun. PATENTANWÄLTE 8000 Munich 2 · Bräuhau »» Street 4 · Telephone Sarnmel No. 225341 · Telegram · Zumpat · Telex S 29979 Gase 1215 12/10 / bs claims 1. Process for the copolymerization of ethylene, either alone or together with one or more α-olefins, and a polyolefin, which contains unsaturated bonds which may be conjugated in high yield, characterized in that the Ethylene and the polyolefin in contact with a catalyst system "brings that consists of 1) a composition made by reacting magnesium metal vapor or manganese metal vapor with a Titanium compound and a halogen donor and 2) an organometallic compound of aluminum. 2. The method according to claim 1, characterized in that one works with a component 1) of the catalyst system, prepared by evaporating the magnesium or manganese or an alloy thereof and then condensing the steam in a diluent containing the titanium compound and optionally the halogen donor. 3. The method according to any one of the preceding claims, characterized in that one works with a component 1) of the catalyst system, which was preferably prepared by subliming the magnesium under vacuum at a vacuum of 266 to 133 x 1CfTPa (2 to 10 "^ Torr) and a temperature of 300 to 65O ⁰ C. 4. The method according to any one of the preceding claims, characterized in that one works with a component 1) of the catalyst system, which was preferably prepared by subliming the manganese under vacuum at a vacuum of 133x10 "" ^ to 133 χ 1cH "Pa (10 ~ ¹ to 10 " ⁴ " Torr) and a temperature of 030039/0685 800 to 110O ⁰ O. 5. The method according to any one of the preceding claims, characterized in that one works with a component 1) of the catalyst: system, which was prepared by condensing the metal vapor in an inert solvent selected from the aliphatic or aromatic hydrocarbons, which is at e ner temperature from -120 to O ⁰ C is kept. 6. The method according to any one of the preceding claims, characterized in that one works with a component 1) of the catalyst: system, the preparation of which at a temperature of
20 to 180 ⁰ C was completed. 7. The method according to one or more of the preceding claims, characterized in that a catalyst system is used in which the titanium compound is preferably the choice is made from the halides, alcoholates, halogen alcoholates or organometallic derivatives of trivalent or tetravalent titanium 8. The method according to one or more of the preceding claims, characterized in that.-the halogen donor is au; chooses from organic or inorganic halides. 9. The method according to any one of the preceding claims, dadurc], characterized in that the organic Halogendonatorverbindun, preferably selects from the chloroalkanes, bromoalkanes, chloroarenes and bromoarenes. 10. The method according to any one of the preceding claims, daduri characterized in that at a molar ratio of the organic: Halogen donor connection to the vaporized metal of equal or: greater than 2 works. 11. The method according to any one of claims 1 to 8, characterized in that the inorganic halogen donor compound is preferably selected from SnCl ,, SbCl., .GeCl. and POCl ₅ . 030039/0685 12. The method according to any one of the preceding claims, characterized characterized in that at a molar ratio of inorganic halogen donor compound to vaporized metal of the same or greater than 1 works. 13. The method according to any one of the preceding claims, characterized characterized in that component 1) of the catalyst system is prepared by reacting the vaporized metal with the lithium compound in an M / Tl ratio equal to or greater than 4 and preferably from 15 to 30. 14. Process for the preparation of high crystalline copolymers according to one of claims 1 to 13, characterized in that ethylene is reacted with a polyolefin, the unsaturated one Contains bonds that may be conjugated. 15. Process for the copolymerization of ethylene with a polyolefin, which contains double bonds which can be conjugated according to any one of the preceding claims, characterized in, that the polymerization reaction is carried out in the presence of an inert solvent. 16. Process for the copolymerization of ethylene with a polyolefin, which contains unsaturated bonds which may be conjugated according to one of claims 14 and 15, characterized in that that one works in an inert solvent which is the same as for the preparation of component 1) of the catalyst composition according to any one of claims 1 to 13 used. 17 includes process for the copolymerization of ethylene with a polyolefin, the double bonds which may be conjugated according to any one of claims 14 to 16, characterized in that one carries out the Pölymerisationsreaktion at a! Cemperatur of 40 to 12O ⁰ C. 18. Process for the copolymerization of ethylene with a polyolefin, which contains unsaturated bonds which may be conjugated, according to any one of claims 14 to 17, characterized in that 030039/0688 net that the polymerization reaction at a pressure τοη e 1 "to about 20" bar (1 to 20 atmospheres). 19. Process for the copolymerization of ethylene with a poly olefin which contains unsaturated bonds that are conjugated can, according to claim 14, characterized in that the ethylene and the polyolefin in the ICatalyst system in gaseous form in the state and in the absence of solvents. 20. A process for the copolymerization of ethylene with a poly olefin containing unsaturated bonds that are conjugated can, according to the preceding claim, characterized in that the reaction is carried out after application or deposition of the Carries out catalyst composition on an inert support 21. Process for the copolymerization of ethylene with a pole olefin containing unsaturated bonds which are conjugated: can, according to any one of claims 9 to 20, characterized thereby net that the reaction is carried out at a pressure of about 1 to about 30 bar (1 to 30 atmospheres). 22. Process for the copolymerization of ethylene with a pole; olefin that contains unsaturated bonds that are conjugated: can, according to one of claims 9 to 21, characterized gekennzeicl net that the reaction takes place at a temperature of room temperature " up to a temperature slightly below the melting point of the copolymer. 23. The method according to any one of the preceding claims, dadur < characterized in that 1,3-butadiene is used as the polyolefin. 24. The method according to any one of the preceding claims, dadurc characterized in that ethylidene norbornene (5-ethylidene (2,2,1> bicyclohepta-2-en) is used as a polyolefin. 25. Crystalline copolymers of ethylene and a polyolefin containing unsaturated bonds that may be conjugated, produced according to one of the processes of the preceding claim 030039/0 68 5 ehe, the reactive unsaturation in the linear macromolecule may contain. 26. Ethylene-iDutadiene copolymer with a ^ C-NMR spectrum with three maximum values or peaks at 32.6, 32.7 and 32.9 ppm, which belong to the methylene groups of the butadiene units. 030039/0685