CS239940B2 - Method of treatment of ethylene copolymeres with minimally one alpha olefin - Google Patents

Abstract

1. Crosslinked material, having improved properties, obtained from copolymers of ethylene and of at least one alpha-olefine, characterized in that its gel factor is between about 95 and 99% and in that the said copolymers are chosen from amongst : (a) ethylene/propylene copolymers which comprise, if appropriate, up to 4 mol% of units derived from another alpha-olefine, have a density of between 0.905 and 0.930 g/cm**3 and a melt index of between about 0.4 and 3 dg/min, possessing from 32 to 62 methyl groups per 1,000 carbon atoms and are such that their density rho, expressed in g/cm**3 , and the proportion m of methyl groups therein are related to one another as follows : 0.9530 =< rho + 0.83 m =< 0.9568, (b) copolymers of ethylene and of at least one alpha-olefine containing at least 4 carbon atoms, the said copolymers having a density of between 0.905 and 0.940 g/cm**3 , a melt index of between 0.2 and 20 dg/min and an average proportion of alpha-olefine units of between 1 and 8 mol%, comprising crystalline fractions and amorphous fractions and having a heterogeneous distribution of the alpha-olefine units, and having a proportion of alpha-olefine units varying between 0.2 and 5 times their average proportion, depending on the fractions in question, (c) compositions comprising up to 40% by weight of an ethylene polymer prepared by free radical polymerization and at least 60% by weight of a copolymer of type (a) and/or of a copolymer of type (b), (d) copolymers of ethylene and of at least one alpha-olefine having from 3 to 12 carbon atoms, the said copolymers comprising from 0.5 to 10 mol% of units derived from the alpha-olefine, modified by the introduction of long-chain branches in such a quantity that their measured limiting viscosity is between 1.3 and 10 times their limiting viscosity calculated from the molecular weight distribution, (e) compositions comprising at least 60% by weight of at least one copolymer of type (a) and/or of type (b) and up to 40% by weight of an ethylene polymer having a specific gravity of between 0.956 and 0.970 and a melt index of between 0.1 and 1 dg/min, (f) compositions containing a mixture of at least one copolymer of type (a) and at least one copolymer of type (b), and (g) compositions containing several copolymers of type (b), more particularly several copolymers having markedly different melt indices, it being possible for the copolymers of types (a) and (b) to be obtained by copolymerization of ethylene and at least one alpha-olefine in at least one reactor comprising at least one zone, at a temperature of between 180 degrees and 320 degrees C and under a pressure of between 300 and 2,500 bars, by means of a Ziegler-type catalyst system comprising, on the one hand, at least one activator chosen from amongst the hydrides and organometallic compounds of the metals of groups I to III of the Periodic Table, and, on the other hand, at least one transition metal halogen.

Description

(54) A method for crosslinking ethylene copolymers with at least one alpha-olefin

Process for the preparation of copolymers of ethylene with at least one α-olefin, comprising _to obtain cross-linked copolymers having a degree of cross-linking in the range of 95 to 99% and improved properties of subjecting said copolymers to a peroxidic compound, characterized in that the peroxidic compound is used in mass 0.5 to 2.5 parts per 100 parts by weight of copolymers and said copolymers are selected from

a) ethylene-propylene copolymers _having an optionally up to 4 molar% structural units derived from yet another a-olefin;

(b) copolymers of ethylene with at least one α-olefin containing at least 4 carbon atoms, with α-olefinic structural units from 0,2 to 5 times their average content in the individual fractions considered,

c) composites containing up to 40% by weight of ethylene sanding by free-radical polymerization with at least 60% strength of type a) olymer and / or b type b) copolymers;

(d) copolymers of ethylene having at least one α-olefin having from 3 to 12 carbon atoms, modified by the introduction of long side chains;

e) komppolce device includes at least 60% of at least one hmotoosi 'copolymers of type a) · and / or b) and at most 40% by weight of the ethylene polymer _in

f) camping out containing a mixture of but one copolymer of type a) with at least one copolymer of type b), and

g) compositions comprising several co-polymers of type b) plus, in particular, several copolymers having significantly different melt indexes.

The co -pooice obtained by the method according to the invention is suitable for conducting a current.

The present invention relates to a process for the copolymers of ethylene with at least one ol-olefin to obtain crosslinked copolymers having a degree of crosslinking in the range of 95-99% and improved properties that allow the use of composites with these copolymers in the production of cables for conducting current.

In the French patent specification δ. 2 · 432 535 discloses a strong crosslinked polymeric polymer content giving a linear ethylene copolymer having a volumetric content of ethylene. before crosslinking smaller than 0.91 ° ^F .cm ^{-3 g} and a content of the bore formed not ^from less mmttylových 30 with ^the clamping on one atom ^of 00 ° Uhl ^ u ^ koi said olce practically free of long chains; its degree of crosslinking, expressed in gel content, is at least 40% and can reach up to 95% ·

U.S. Pat. No. 3,105,057 discloses a copolymer comprising an ethylene-1-butene copolymer comprising 1-butene in a 5 to 30% by weight, a finely dispersed filler and an organic peroxide crosslinker.

U.S. Pat. No. 3,173,903 discloses a process for crosslinking ethylene copolymers having a propylene density of less than 0.92 and a mercury content of 7 to 20% propylene prepared in a homogeneous liquid phase at a pressure of less than 10 M @ 2 and a temperature lower than 85 using a mixture of peroxide with carbon black.

It has now been found that by replacing the known materials with a copolymer of ethylene with at least one ethylene-derived copolymer as described below, the degree of gelation of the crosslinked polymer is increased.

SUMMARY OF THE INVENTION The present invention provides a process for crosslinking ethylene copolymers with at least one [beta] -lefinine to obtain crosslinked copolymers having a degree of gelation in the range of 95-99% by subjecting said copolymers to a peroxidic compound, characterized in 0.5 to 2.5 parts per 100 parts by weight of copolymers and said copolymers are selected from the group consisting of:

a) copolymers of ethylene with propylene, optionally containing up to 4 ^ C ^ ^ oíár: í% structural ^d is derived from the note ^to another j.eš ^ ^u lΛ ole ^{f-ins on} objeοov ^{E U]} · οol8nilti ^0.90 to 5 ^0.930 g.cm "', ^and flow Ndex tavenipy about ^0, 4 ^and 3 dg.min' ¹ and content ² and 3 ^{from 62} mettylových groups per ¹⁰⁰⁰ atoms ^at 1 ^^ ^p ^ 1 Rice refrigerati ^{f h b} of Jem ΒΟ ^ ^ * ^ βΙ expressed in GC ^ ^-3, the ^p OCD and I ^ ttylových groups per 1000 carbon, will be recovered in the relation 0.9530 vzdema ^^ - ^ + 0.83 0.9568 m-,

b) copolymers of ethylene with at least one «^ -oleate nem containing at least 4 carbon atoms, wherein these by-koptymery 'my notes in density ^{of 0.905 M} and ^0.940 g.cm ^-3, ex ^d in that ^the melt at ^0, 2, and ^{z 20} dg.min ^-1 and ^H contained středd 8tru ^the current ^I-cUjt Hférových Notek ^d is ^{1 and 8} could ^{^%,} content;)! crystalline and ammonium fractions, and eject heterogeneous oleff of the new structural units, wherein the content of the structural units varies from 0.2 to 5 times their mean content in the individual fractions considered,

(c) accomplices. up to 40% by weight of a polyethylene obtained by a free-radical polymer with at least 60% by weight of copolymers of type a) and / or copolymers of type b),

d) copolymers of ethylene with at least one olefin having from 3 to 12 carbon atoms, containing

0.5 to 10 molar% of the olefin-derived structural units, these copolymers being folded by introducing long side chains to such an extent that their measured viscosity limit is 1 of their viscosity limit number calculated from the molecular molecular distribution,

e) komppoice obsáhnuJící least 60% hmolnοlSi least one copolymer of type a) and / or type ^{u nane} j ⁱⁿ YS ^40% ^ ο ^ οθ ^ after ^l y '^ ru ettylenu density ^{of 0,} 95 ⁶ to 0.970 and a melt index ^{0 ,} 1 to ^{1 dg} .min ^-1,

f) a composition comprising a mixture of at least one type a) copolymer with at least one type b) copolymer, and

g) comprising several copolymers of type b) plus, in particular, several copolymers having significantly different melt indexes.

The other α-olefin optionally present in the copolymers of type a) and the «-olefin used in the preparation of the copolymers of type b) is preferably a *-olefin containing from 4 to 10 carbon atoms. Such an A-olefin is, for example, 1-butene, 1-hexene, 1-octene and 1-decene.

The copolymers of types a) and b) are preferably obtained by copolymerizing ethylene with at least one olefin in at least one reactor containing at least one zone, at a temperature of 180 to 320 ° C and a pressure of 30 to 250 ° C, using: The Ziegler-type catalyst systems comprising at least one activator selected from the group consisting of hydrides and organometallic compounds of the metals of the first to third groups of the Periodic Table and halogenated transition metal compounds. '.

The copolymers of type a) preferably have a number average molecular value. 10,000 to 28,000 and a polydispersity index (ratio of the mass median molecular weight to the numerical median mass measured by geography by gel) of 7 to 14. Preferably, they are obtained by co-polymerizing ethylene with propylene in at least one reactor containing at least one reactor containing at least 180 to 320 ° C and a pressure of 30 to 250 MPa using a catalyst of the Zegler type comprising at least one activator selected from the group consisting of hydrodes and organometallic compounds of metals of the first to third groups of the Periodic Table and at least one halogenated transition metal compound wherein the gaseous feed to the reactor is in a stationary state consisting of 65 to 85% ethylene and 65 to 85% propylene. 15 to 35% and the halogenated transition metal compound comprises a complex compound of the formula (%%) (MgX ₂ ) γ (AlCl-Pa (W) b in which

M is a metal selected from the group consisting of titanium and vanadium,

X is halogen and

R is a hydrocarbon radical, wherein for the general symbols 2, χ, 2 and Js,.

4 and S 3, 2 4 í 20, 0 3 1 / a 3 and ^ f f.

The copolymers of (b) preferably have a number average molecular weight of 15,000 to 60,000 and a specificity index of 3 to 9. Their crystalline fractions may, in differential theimic analysis, have a single maximum corresponding to their melting at 118 to 130 ^σ 0, and may represent 20 to 50% of the total hmoonootic type b). The copolymers of type b) may contain structural units derived from two .alpha.-olefins, the mean diameter of these olefins being 0.25 to 4. In the latter case, the copolymers of type · b) preferably have a polydispersity index of 6 to 12.

The copolymers of type b) are preferably prepared by copolymerizing ethylene with at least one olefin having at least 4 carbon atoms in at least one reactor containing at least one zone, at a temperature of 180 to 320 ° C. and a pressure of 30 to 250 MPa using a Zieg-ers type catalyst system comprising an activator selected from the group consisting of hydrides and organometallic compounds of the first to third groups of the Periodic Table of the Elements, and at least one halogenated compound of the precursor metal; the transition metal is 1 to 10 and the mean residence time of the catalyst system in the reactor is 2 to 10

100 seconds; the gaseous feed to the reactor consists of ethylene in the top of the reactor. 10 to 80% in a stationary state and from the rt-slurry in a weight ratio of 10 to 80%; 20 to 90%, and the catalyst system has a higher reactivity to ethylene than to ω-olefins.

An example of such compounds has the general formula (TiCl ₃ , 1/3 AlCl ₃ ) (MX ₃ ) _x (MgCl ₂ ) _y , in which

M is a transition metal selected from the group consisting of metals of the fifth sub-group, the sixth sub-group and the eighth sub-group of the Periodic Table of the Elements,

X is 'halogen' and for the general symbols χ and χ,

0.3 * x * 3 and O 4 y 20.

ii «<

The term gaseous feed to the reactor in a stationary state is understood to mean the average composition of the feed to the reactor, it being understood that the composition is not the same at individual locations in the reactor and that it can vary along the reactor, especially if the reactor contains several zones. This composition varies depending on the nature of the α-olefin contemplated. In the case of a binary copolymer, the ω-olefin content of the feed to the reactor is preferably 15 to 70% by weight for 1-butene and 35 to 90% by weight for 1-hexene. In the case where a multi-zone reactor is used in the process according to the invention, it is most often preferred that the main amount of ol-olefins is injected into the first zones operating at 180 to 240 ° C, while in the last zone the temperature it maintains in the range of 240-320 ° C and does not introduce a more substantial amount of α-olefins.

The ethylene polymers with at least one ε-olefin of type d) are preferably prepared by a process comprising copolymerizing ethylene with at least one ε-olefin in at least one reactor in the presence of a Ziegler-type catalyst system at a temperature 180 DEG-320 DEG C., a pressure of 30 to 250 MPa and a residence time of the catalyst system of 1 to 120 seconds, after which the copolymer obtained is heated in the presence of 0.01 to 1 ml of at least one free radical initiator per kg of copolymer at 220 to 320 ° C for 5 to 200 seconds at a pressure of less than 100 M ?. This pressure is chosen to prevent polymers, unreacted monomer and thus the formation of low density polyethylene by radical polymerization.

The o-01efin is added as such to the reactor or is formed by oligomerization of ethylene.

The content of 4-thiophene in the reaction network depends on the nature of the n-oil: it is preferably 15 to 35% by weight of propylene, 5 to 65% by weight for 1-butene and 5 to 80% by weight for 1-hexane. This composition is not necessarily constant over the length of the reactor.

The contacting of the resulting copolymer with at least one free radical conducting agent may be effected by spraying a solution or suser of the free radical initiator into the last reaction zone of the reactor or series of reactors, wherein the printing in this reactor is less than 100 MPa. a separator operated at a pressure of 5 to 50 MPa downstream of the reactor, the function of the separator being to separate the formed copolymer from the unreacted mono. Mixing with the die can also be carried out in a processing machine such as an extruder operated at a pressure of 0.1 to 2.5 MPa, it is known that the pressure in the extruder can reach up to 25 MPa according to the extruder screw conveyor profile. The mixing of the free radical initiator with the copolamer in the processors of the machine is preferably carried out in the case where a LiL solution or dry-prepared premix is used.

According to a preferred embodiment, the crosslinked compositions according to the invention can be obtained from salts, on the one hand, a copolymer of ethyl with an α-olefin of type a), and, on the other hand, an ethylene polymer obtained by free-radical polymerization. Preferably, said ethylene polymer with a free-radical polymer has a bulk density of 0.91 · 0.94 g · cm · · ·. · Prepare polymmraci ethylene under high ^{5 239940} pressure and high temperature in the presence of an initiator uncommited radicals. The polymerization of ethylene can be carried out in the presence of a small amount of at least one monomer copolymerizable with carbon monoxide, such as carbon monoxide, an ethylenically unsaturated carboxylic acid, an ester derived therefrom and a C 1 -C 8 alcohol, anhydride maleic acid and vioylacetate.

The paddles of another preferred embodiment of the present invention may be crosslinked compositions of type e) comprising at least one copolymer of type a) and / or b) at least 60% in the masculine age, and ethylene polymer of density 0.956 to 0.970 and melt index ^0.1 and ^z i ^d .mLn ^'1 bnmtnostním ° at most 4%. The ^P copolymer & generally homopolymers of ethylene, called high density polyethylene, which can be made spills known polymerization procedures, especially at elevated pressure and temperature which several variations embodiment is described in the French patents and, 2,346,374, 2,399,445, 2 445 343 and 2 445 344. This so-called high-density. preferably polyethylene has a broad molecular weight distribution and has a polydispersity index, for example, of 8 to 18. Component type e) has a density of 0.910 to 0.940.

Κοπ ^ ζί-type G), for example SPOS two Copolymers of ethylene B - L-buteneia, rnaaící in ^d ex melt ^Y 5 ^and 10 dg ^ in ^- ', and obtained from ^ polymers thereof in ^d ex melt is close to 1 to ^{20 dg} .mio ''.

The crosslinking compositions prepared by the process of the invention may contain fillers, for example gas, oxides, carbonates or metal sulphates, anticidal agents, lubricants and pigments.

They are obtained by treating the polymers of ethylene with at least one polyphosphine used as starting materials with a peroxide compound selected from benzoyl peroxide-containing group, dicumperoxide, 1,3-bit (tert-butylisylisopropylisyl) -butyl, ditsroxylbutyl. (N-amyl peroxide, larylsyl oxide and their relative to each other in the range of 0.5 to 2.5% relative to the mono-mono-morphology of the polymer to be crosslinked. The crosslinking is generally carried out at a temperature of 180 to 250 ° C after The crosslinking can be carried out under pressure or in a bath of molten salt.

The crosslinked compounds produced by the process of the invention find a wide application in the production of power cables.

The invention will be explained in more detail below with reference to examples of a specific embodiment. All parts herein, unless otherwise indicated, are HP parts.

The obtained duplicates were subjected to Assays

- the degree of gelation according to ASTM D-2765/72, expressed as a percentage of hmoonnosi,

- creep degree according to UTE 33209, expressed as a percentage,

percentage elongation at break according to NFC 32101, expressed as a percentage, and

- ^ οβο ^ Οη ^ © extension according to HN 33523 and CEI 53Θ, expressed as a percentage.

He did

A copolymer of ethylene and propylene - type (a) having the following properties was used:

volumetric hmoonoot: ^0.905 g / cm ^J content of propylene structural units: 12% melt index: 3 dg / mio number of methyl groups and 1000 carbon atoms: 60

And prepared by copolymerizing ethylene and propylene in a cylindrical autoclave operated at 120 MPa and equipped with stirrers and metal baffles delimiting three zones of equal volume in the autoclave. Zone 1, maintained at 220 ° C, is fed at a rate of 40 kg / h ethylene at a rate of 30 kg / h propylene; this zone comprises a catalytic system comprising, on the one hand, mixed TiGl ₃ , 1/3 AlCl ₃ and, on the other hand, trioctyl almainix in such an amount that the atomic ratio Al / Ti is 3.

Zone 2, maintained at 240 ° C, is fed with ethylene at a rate of 20 kg / h and contains no catalyst.

Zone 3 at which the copolymer-containing reaction mixture is discharged to a separation and recycling plant is maintained at 260 ° C and fed with ethylene at a rate of kg / h; this zone comprises a catalytic system comprising both complex compounds of the formula

TiCl ^ 1/3 AlCl 3, 6 #gCl ₂ obtained by grinding the mixed chloride TiClj 1/3 AlCl ^ anhydrous chloride čnatým mount and, secondly dimetluУeelwtHetJlut-siloxalao mnnoství in such that the atomic ratio Al / Ti is equal to 3. Copolymerization is carried out in the presence of 0.1% by volume of hydrogen.

To 100 parts of the copolymer obtained were added 50 parts of carbon black. and the mixture is stirred in a mixer at 80 ° C for 3 minutes; 1 part of 2,2,4-trimethyl-1,2-difluorosulphonium polymer (hereinafter referred to as the oxidizing agent A) and 5 parts of 1,3-phthalene (1-methylthiol) are added to the obtained mixture. 1-dimethyl urethane (hereinafter referred to as oeroxide P) with a concen- tration of the active substance of 40% by weight. (or 2 parts pure peroxide) and mix the resulting mixture in a mixer at 120 ° C for 5 minutes. .

The resulting mixture was cross-linked at 3.5 MPa and 180 ° C for 12 minutes.

Its gelling, flow rate (15 min, 150 ° C and 0.2, 0.4 and 0.7 MPa) and retentive elongation were determined. In addition, the time t in seconds necessary to achieve a degree of gelling at a temperature of 185 ° C of 90 ° was measured using an optimizer Μ. I. E. type

Example 2

A heterogeneous polymer of ethylene and 1-butene of the type (b) described above has the following properties:

a ^ ^b © Jem kidnapping .: ^0.918 g / cm ³ a melt index of 0.8 dg / min, the 1-buenových structural units: $ 3.4 number-average molecular hϊnoSnost: 43,000 polydispersity index: 3.6 m ^^ OZS ^ ¹ ^: lateral methyl groups per 1000 carbon atoms: 17, melting point of the crystalline fraction 122 ° C, the heterogeneity of distribution of 1-butene: according to the considered fraction from 0.5 to 2.2-riásobek secondary content.

This copolymer was prepared in a cylindrical autoclave operated at 90 M 2 and equipped with a stirrer and metal baffles that divide the interior of the autoclave into three zones.

Zone 1, maintained at 210 ° C, has twice the volume of each of the two successive zones; to this zone a mixture containing 36,515 of 1-butene and 64% by weight of ethylene is fed at a rate of 200 kg / h, and the zone comprises a catalytic system comprising both di-butene-lithium fluorosilane and a compound of formula ₃ , 1/3 and ₃ , VCI _{3 7 239940} in an amount such that the atomic ratio Al / Ti is equal to the third

Zone 2, maintained at 240 ° C, is fed at 55 kg / h with the same mixture as is fed to zone 1, and this zone also contains the same catalyst.

Zone 3, at the exit of which the copolymer-containing reaction mixture is discharged to a separation and recycling plant, is maintained at a temperature of 280 ° C and is not introduced into it by either monomer or catalyst. The mean residence time of the catalyst system in the autoclave is 43 seconds.

The copolymer obtained is crosslinked under the same conditions as in Example 1.

EXAMPLE 3 An ethylene, propylene, and 1-butene terpolymer of type (a) prepared under the conditions described in Example 1 is used, replacing one fraction of the propylene gas feed with 1-β-1; This terpolymer has the following characteristics:

volumetric hmoosnoot: ^0.906 g / cm ³ melt index: 0.7 dg / min number of side alkyl groups per 1,000 carbon atoms: 47 content of yarns of structural units: 7 µm / cm @ 3 1-butene structural units: 2.4.

This terpolymer was crosslinked under the conditions of Example 1.

The values measured for Examples 1 to 3 are summarized in the table below.

Table 1

Example t Degree of gelling Degree of teenie 150 ° C, 15 min (%) 8emnnon elongation (%) (with) (%) 0.2 MPa 0.7 MPa 0.2 MPa 0.7 MPa 0.4 MPa 0.4 MPa

1 250 96 4 8 28 0 8 28 2 192 97.8 0 12 12 0 0 12 3 184 97 0 8 8 0 8 4

Examples 4 and 5

The copolymer of Example 2 and the terpolymer of Example 3 were crosslinked under the following conditions. .

To 100 parts of polymer is added 0.55 parts of antioxidant A and 32 parts of peroxide P containing 40% active ingredient (or 1.28 parts of pure peroxide P) and mixed in a mixer for 5 minutes at 120 ° C. ®C. The sweat mixture is thickened at a pressure of 3.5 MPa and a temperature of 180 ° C for 12 minutes.

The results of the measurements are shown in Table II below.

Table II

Example t (with) Degree of gelling <%) Degree of creep 150 ° C, 15 ° C («) 0.2 MPa 0.4 MPa RemoaonOther extension C%) 0.2 MPa 0.4 MPa 4 186 97.3 4 24 0 4 5 182 95.7 8 20 May 0 0

Examples 6 and 7

To 100 parts of the copolymer of type (a) described in Example 1, under the conditions described in Examples 4 and 5, are added: 0.5 parts of antioxidant composition A and the amount of Pure peroxide P shown in Table III below.

The amplification is carried out at 180 ° C with a contact time of the components of 12 minutes. Thereafter, the properties of the obtained cross-linked cooppoic are measured. The degree of creep was measured ⁿ pM ^0.2 MPa and ²⁰⁰ ° C.

The measurement results are shown in Table III below.

Table III

Example Peroxide P Grade zgeltvatěoí (%) Degree of creep. 0.2. MPa, 200 ° C 16 oio («) Reoan. prodl. (%) t with (parts.) 6 0,935 96.6 15 Dec 688 223 7 1,25 98.2 10 602 214

Claims (9)

OBJECT .. OF THE INVENTION CLAIMS 1. A process for crosslinking ethylene copolymers with at least one polyolefin to obtain crosslinked copolymers having a degree of crosslinking in the range of 95 and 99% and improved properties of subjecting said copolymers to a peroxidic compound. Characterized in that the peroxidic compound is used in an amount of from 0.5 to 2.5 parts per 100 parts by weight of the copolyomer and said copolymers are selected from the group consisting of: (a) copolymers of ethylene with propylene, optionally containing up to 4% by volume, of a percentage of the structural ions derived from another α-olefin. ^ o ^ wears ^0.905 to ^{0.930 g} .cm ^{"3 Ind} exe ^m ^ to ^ ^{and t} ^ ⁱ ^ oy Veo ^{0.4 and} 3 dg.oin. ¹ and containing from 32 to 62 butterfly groups ^of about ^10,000 and ^10,000 carbon atoms, and having a volume ratio of about ^{10,000 to} about ^10,000 . expressed in g.cm &^lt; ^{3 &gt}; and having a number of methyl groups per 1000 carbon atoms having a relationship of 0.9530 ± 0.83 m to 0.9568, b) kopolyoery ethylene with at least one My-olefOneo containing at least 4 carbon atoms, PRICE tyW ° ^{F to} about opolyoery ooaí ^ emove weight of ^{from 0.905} to ^{0.940 g} cm @ ^-3>, a melt index of ^{0.2 to 20} dg.oio ^'1 and last but content structures ° - ~ ^f оoe structure where units ^1-8 oooárnfch%, comprising crystalline fractions and aooofoí and vylkaaují. heterogeneous distribution of the structural units, the content of the &lt; - &gt; IN* 0.2-fold to 5-fold their mean content in each fraction considered,. (c) compositions comprising up to 40. % by weight of polyethylene obtained by radical polymerization; at least 60% of the hIDO0OoSi of the copolymer of type a) and / or the polymer of type b), d) ethylene topolymers with at least one C0-C12 olefin containing 0.5 to 10 molar% of the odd-ooeine-derived structural units, the copolymers being characterized by the introduction of long side chains in such that their measured viscosity limit number is up to 10 times their viscosity limit calculated from the distribution mooculum, ^ ο ^ ο ^ Ι, e) a thermo-content comprising at least 60% by weight of at least one type a) and / or type b) polymer and at most. 40% by weight of an ethylene polymer having a density of 0.956 to 0.970 and a melt index of 0.1 to 1 dg / min. f) a copolymer comprising a mixture of at least one polymer of type a) with at least one polymer of type b), and g) a composite comprising several polymers of type b) plus, in particular, several polymers having significantly different melt indexes. 2. Method. 4. The process of claim 1 wherein the additional ω-olefin is an olefin having from 4 to 10 carbon atoms. 3. A method according to claim 1, wherein the copolymer of type a) is of the type having a number average molecular weight of 10,000 to 28,000. 4. The process according to claim 1, wherein polymers of this type having a number average molecular weight of 15,000 to 60,000 are used as type b) polymers. 5. The process according to claim 1, wherein the copolymers of type a) are polymers of this type having an olefin density index of 7 to 14. 6. The process according to claims 1, 2 and 4, characterized in that polymers of type b) are used with polymers of this type having a polyolefin index of 3-9. 7. Process according to Claims 1, 2, 4 and 6, characterized in that crystalline fractions of polymers of type b) having a single maximum melting point at 118 DEG to 130 DEG C., which represent 20 to 50% of total UmotnottaíUo оп ^ Ху! of type b) polymer. 8. The process of claims 1, 2, 4, 6 and 7 wherein the polymers of type b) are copolymers of this type. of the type comprising the structural units derived from the double olefins, having an average content of 0.25 to 4. 9. The process according to claim 8, characterized in that, as type b) polymers, the polymers are indexed. 6 to 12.