DE2123297A1 - Copolymer of olefins or olefins and non-conjugated dienes with unsaturated derivatives of furan and / or thiophene and process for its preparation - Google Patents

Description

Dipl.-Ing. OJpI.oee. publ. _{1 1} ,,. _1n71 DIETRICH LEWINSKY ^{11 iial 1971}

PATENT AGENT ⁶⁵⁷⁷

Telephone 56 \ 7 62

6 Nationale des Pltroles d'Aquitaine, Courbevoie (France)

"Copolymer of olefins or olefins and non-conjugated dienes with unsaturated ones Derivatives of furan and / or thiophene and Method of its manufacture "

Priority from French patent application No. 70/170 16 of May 11, 1970

The invention relates to copolymers of olefins, especially of alpha-gleefins, or of olefins and non-conjugated ones Serving with unsaturated derivatives of furan or thiophenes. It also relates to a process for making such copolymers and, if these copolymers are elastomeric in nature, their vulcanization and the vulcanized thereby obtained Blastomeres.

Bs is known to olefins and especially alpha-olefins or Polymerize olefins and non-conjugated dienes at low pressures or to copolymerize, with the help of kata-! lytic coordination systems, which are created by combining compounds of the elements of subgroups IV to VIII of the periodic table of the elements with organometallic compounds formed by elements of groups I to III of this system will.

109848/1771

It is also known that such catalytic systems make it possible to copolymerize alpha-olefins with certain ethers or thioethers which have an alkenyl substituent whose double bond is preferably in the ^ω- position.

It has now been found that interesting copolymers of olefins, especially of alpha-olefins, or of olefins and Non-conjugated dienes can be obtained with certain unsaturated derivatives of furan and / or thioppn, namely by copolymerization with the mentioned catalytic coordination systems.

The copolymers according to the invention are prepared by bending one or more olefins together or optionally one or more non-conjugated dienes with one or more unsaturated compounds of furan or thiophene, those of the general formula

- (COO)

• -Π

correspond, in which X denotes oxygen or sulfur, ρ is 0 or 1 and R ^, when ρ = O, a vinyl radical or

represents, where m is an integer between 0 and 12, and, when ρ = 1, an alkenyl radical with 2 to 20 Represents carbon atoms, in the presence of a catalytic coordination system from an organometallic Compound (A) of one or more metals of groups I, II or III of the periodic table and a compound (B) one Transition metal of groups IV to VIII of this system.

109848/177

The olefins which can be copolymerized by the process according to the invention can have 2 to 1δ carbon atoms. Bs are especially alpha-glyphins of the general formula R-CII = CIi ₂ , in which R is hydrogen or an alkyl, aryl, cycloalkyl, alkylaryl radical, and especially linear alpha-olefins such as ethylene, propylene, butene-1 , Hexene-1, octene-1, the most common are ethylene, propylene and butene-1.

The non-conjugated dienes copolymerizable according to the invention can be linear or cyclic. Particular mention should be made here of 1,4-hexadiene, dicyclopentadiene, tricyclopentadiene, 1, S-cyclooctadiene, 5-ethylene-2-norbornene, S-ethylidene-2-norbornene, etc. ^r .

As compounds of furan or thiophene, which one with the olefins or with the olefins and the non-conjugated dienes can copolymerize, are to be mentioned.Vinylfuran, the adduct from vinylfuran to cyclopentadiene, furfuryl undecylenate, furfuryl dodecenate, Furfuryl octadecant etc .; In addition, the unsaturated heterocyclic radical can be used one or more times be substituted with alkyl, aryl, cycloalkyl, alkoxy, aryloxy and dialkylamino radicals which have 1 to 16 carbon atoms may have, or with halogens.

The copolymers produced by the process according to the invention have such a high molecular weight that they are solid at normal temperature. They are essentially linear and can vary be thermoplastic or elastomeric according to the nature and proportional amounts of the monomers used. These Copolymers are highly resistant to decomposition by ultraviolet light and by thermal oxidation. .

The thermoplastic copolymers are well suited for shaping in the thermoplastic state by extrusion and compression molding for the production of films, fibers, foils, profiles, etc.

109848 / 177S

BATH ORIGINAL

2125297

The copolymers based on ethylene can be used, for example, in the manufacture of cables used for insulation purposes.

^{The elastomeric copolymers can be vulcanized 1} with the aid of compounds which form free radicals, such as peroxides or sulfur, if they contain diene units. The vulcanized copolymers have excellent mechanical properties, combined with a high resistance to decomposition by ultraviolet rays and by thermal oxidation, and can be used, for example, in the manufacture of seals in the building industry, conveyor belts, etc. j

The copolymers according to the invention contain 99.9 to 751; preferably 99.5 to 85% by weight of non-polar olefinic. or optionally dienic units, and 0.1 to 2½%,! preferably 0.5 to 15% by weight of polar units of the derivative or derivatives of furan and / or thiophene.

In applying the invention to the production of elastomers containing ethylene, the lower limit for the ethylene content is not determinative, but the upper limit should preferably be 75% by weight in order to avoid crystallinity of the polyethylene type. The proportion of the second olefin | particularly an alpha-olefin, can \ acids, such as propylene, butene-1, or the second I olefin and the nonconjugated diene in the copolymerizable * between 5 and 75 wt * lie., the content of diene followed by non-· jugiertem can be between 0 and 20% by weight, the amount of polar monomers between 0.1 and 201, preferably between 0.5 and 15% by weight.

Catalyst systems which are particularly suitable for the preparation of the copolymers according to the invention are formed by Combination of organic aluminum compounds with compounds of titanium, vanadium, zirconium, tungsten etc., e.g. halides,

$ 109 848 / $ 177

212329?

Oxihalides, compounds in which at least one valence of the Transition metal is saturated with a heteroatom, especially oxygen or nitrogen, linked to an organic group, such as acetylacetonates, benzoylacetonates, alcoholates. In some cases it is advantageous to use a complex of the derivative of

Use transition metal with a ligand such as an aliphatic ether, liie diethyl ether, dipropyl ether, diethoxyethane, etc., a cyclic ether, such as tetrahydrofuran, dioxane, etc., thioethers, phosphines, arsines, tertiary amines, such as trimethylamine, methyldiethylamine, etc., heterocyclic nitrogen bases such as pyridine, quinoline etc., ß -diketones, ketoesters, hydroxyaldehydes, amino aldehydes, amino alcohols etc.

Excellent results are obtained from using a catalyst system used, which consists of an organoaluminum compound of the formula AlCl, -% Y_, in which η 1, 1.5, 2 or 3 and Y is a is a lower alkyl radical such as ethyl, propyl, isobutyl, etc. combined with a halide of titanium such as titanium trichloride, or titanium tetrachloride, or with a halide or an oxyhalide of vanadium, such as vanadium trichloride, vanadium tetrachloride or vanadium oxitrichloride, said halides of titanium or vanadium, optionally in complex form with tetrahydrofuran, an aliphatic ether, a tertiary ether Amine, pyridine or quinoline can be present.

The catalyst can also be applied to a support or be chemically bonded to it, this support being both can be organic or inorganic.

The catalyst system can also contain a certain proportion of an activator, especially a halogen sulfite or an iialogensulfate of an alkoxyalkyl, such as chlorosulfate or chlorosulfite of ethoxyethyl, or of a Halogensulfinyl- or a Halogensulfonyl-thiophens such as di- (chlorosulfonyl) -

109848/1778

2,4-th'hiophene, or a dichloroarylphosphine such as dichlorophenylphosphine.

To form the catalyst system, the compounds (A) and (B) are mixed or not mixed before they are introduced into the reactor. The catalyst can too

to be preformed or, where appropriate, "aged", are then '■ zu.polymerisierende mixture is introduced continuously or discontinuously into di. ^"3

! If an activator is used, it can be added to the catalyst before the ™, introduction to be added to the reaction mixture; one can also introduce the activator directly into the mixture during the polymerization, continuously or partially; at another

; whose mode of operation you first mix the activator with the compound (s) of the transition metal (s).

The catalyst system consists of such amounts of the compounds A and B, that the atomic ratio of the metal of the connec-! dung A to the transition metal of compound B between 1 and 50, is preferably between 3 and 30.

The amount of activator used can vary widely. zen can be varied. In particular, 0.5 to 25 moles of activator per gram atom of transition metal are used, but it is necessary that the reaction mixture contains more of the compound A, expressed in gram atoms of the metal, than activator.

The copolymerization is carried out in a suitable solvent, which is preferably an aliphatic, aromatic or cycloaliphatic hydrocarbon, such as heptane, cyclohexane, benzene, or mixtures thereof Solvent. It is also possible to use halogenated hydrocarbons which are inert to the catalyst, e.g.

109848/1776

Chloroforia, chlorobenzene, tetrachlorethylene, etc. The olefins themselves can serve as solvents, and the copolymerization can
For example, in the one or more liquid olefins are carried out _; which are to be copolymerized. " \

The copolymerization can be carried out j +110 ⁰ C, at temperatures between -80 and, but there are temperatures between -30 and +60 j is preferably ⁰ C.

The pressures generally used during the copolymerization are between 1 and 10at, but it is possible
to work even at higher pressures.

The proportion of polar monomers that is brought together with the olefins, is chosen so that the copolymer between 0.1

and 25% by weight of units of these monomers. I.

The polar monomers is generally introduced on einemal in the re \ actuator, before the addition of the catalytic \ Systems. However, it is also possible to partially continuously or discontinuously admitting this monomers wholly or '· during the polymerization. :

In certain cases it can be advantageous for the polar monomer in the polymerization mixture to be in the form of a complex ■ with a Levis acid such as, for example, aluminum trialkyl, dihalo; aluminum alkyl, aluminum halide, zinc chloride, tin tetrachloride, ¹ , etc. is present. Said complex can be formed in situ in the reaction mixture, or it can be formed prior to its introduction into | the polymerization zone are produced. I.

The copolymerization can be carried out continuously,
in this case, the solvent, the monomers and the catalytic .scLe system are continuously fed into the polymerization zone in the
Ma> e introduced that their residence time in this zone is sufficient '' ■

1 09848/1776

BATH ORIGINAL

-i 8 -

list, the desired concentration of copolymers in the reaction \ mixture to achieve.

I When carrying out the copolymerization, the reaction mixture is passed through an inert gas such as nitrogen, Argon, deoxygenated before polymerization.

The duration of the copolymerization generally depends on the Working conditions. It is usually between 30 minutes and ι 3 hours.

»At the end of the operation, the catalytic converter is destroyed in the In this way, the copolymer is removed from the solvent by coagulation with an alcohol, by evaporation of the solvent Ior separated in any other way! which allows a polymer isolate from its solution.

I The invention is illustrated in more detail by the following examples ! purifies.

! example 1

j The copolymerization takes place in a cylindrical glass reactor

i with an inner diameter of 10 cm and a volume of

1000 ml carried out, which is equipped with a stirrer, a dropping funnel for introducing the heterocyclic monomer, jtwo dropping funnels for introducing the catalytic system and .Gas inlet and outlet pipes. The temperature inside the Reak-i tor is kept at 10 C with a thermostatically controlled bath in which the reactor j is located. |

! The dropping funnels above the reactor are filled with nitrogen

j rinses. In the dropping funnel to introduce the heterocyclic;

Monomers are filled with 60 millimoles of vinyl foran. In one of the drip '

1 millimole of vanadium is added to the funnel for the catalytic system!

itrichloride in 50 ml of anhydrous n-heptane, in the other 30 \

Nillimole diethylaluminum chloride Al (C ₉ Hc) ₇ Cl in the _ft '.

1098A8 / 177S

BATH ORIGINAL

- 9 same fifty n-heptane.

750 ml of n-heptane, which has previously been dried and degassed, are placed in the reactor, which is kept under nitrogen. The nitrogen is turned off and a mixture of ethylene and hydrogen in an alcoholic ratio of 3: 1 is introduced through the gas inlet pipe, in a total amount of 100 standard liters per hour for the entire duration of the copolymerization. 20 minutes after the start of the introduction of the gas mixture, the vinylfuran and the constituents of the catalytic system are added dropwise over the course of 60 minutes. After the addition of the catalysts, the polymerization is stopped by adding 20 ml of ethanol. The solution of the copolymer is poured to precipitate in ethanol, then washed with ethanol and dried in a vacuum drying cabinet at about 50 to 60 ⁰ C.

23 g of a crystalline product are obtained whose viscometric molecular weight is about 51,000 and which has a melting point of 133 ^° C. and a melt index of 0.1.

The copolymer of ethylene and vinyl furan contains 97.8I ^ Ethylene and 2.2% by weight vinyl furan.

Example 2 \

Example 1 is repeated, the heptane being replaced by Ben- ' zol, vanadium trichloride through 1.5 millimoles of a complex j replaced by vanadium trichloride with 3 moles of tetrahydrofuran and 45 millimoles of diethylaluminum chloride are used.

This gives 33 g of a crystalline copolymer of ethylene and vinyl furan having a molecular weight of about 49 000, a melt index of 0.2 and a melting point of 134 ⁰ C. This copolymer contains 2,4.Gew.I vinylfuran.

Example 3

- 10 -

109848/17761 BAD ORIGINAL

- ίο -

Following the procedure of Example 2, the vinylfuran is replaced by 25 millimoles of the adduct of cyclopentadiene and vinyl ·; furan

which is added all at once changes the molar ratio of ethylene: hydrogen to -1.5: 1 and uses 1 millimole of the complex VC1 ~. 3 tetrahydrofuran and 30 millimoles diethyl aluminum chloride the catalysts being added in 40 minutes.

'■■%

25 g of a crystalline copolymer from 97.5 are obtained ^! Ethylene and 2.5% of the adduct of cyclopentadiene and vinyl furan.

Example 4

The procedure of Example 3 is repeated, but the mixture of ethylene and hydrogen is replaced by a mixture of Propylene and ethylene in a molar ratio of 1.2: 1 and used as catalysts 2 millimoles of vanadium trichloride and 10 millimoles of diethyl aluminum chloride.

After drying, 13 g of a solid product are obtained which looks like a non-vulcanized elastomer. This Copolymers contains 41% ethylene, 56.1% propylene and 2.9% des Adduct of cyclopentadiene with vinyl furan.

Vulcanization:

100 parts of the Gettficht parts obtained are mixed in a roller mixer Copolymers with 60 parts of carbon black IIAF, 5 parts of zinc oxide, 0.32 parts of sulfur and 6.75 parts of dicumyl peroxide (40%).

The mixture is then in a press at 1C0 ° C for 1 hour heated.

- 11 -

109848 / -177S

Mechanical properties of the vulcanized product:

tensile strenght 210 kg / cm ² Stretch glue tearing 3203 Young's modulus at $ 300 expansion 190 kg / cm ^l Shore Markets A 74 Rebound 62%

Example 5

The procedure of Example 1 is repeated, the vinyl furau is replaced by 25 millimoles of furfuryl octadecenate [CL ₅ -CCIi ₂ ) ₇ -Cli = CiI-CCh ₂ ) ₇ -COoJ Π J, the wood ratio is established

Ethylene to hydrogen to 5.25: 1 and used as catalysts 2 millimoles of the complex VCl, .3 tetrahydrofuran and CO Millimole Diet ^ ylaluminum chloride.

This gives 54.7 g of a crystalline product under X-rays, which has a molecular weight of 82 000 viskosiinetrisches, a Schmelziiiuex of 0.66 and a melting point of 132 ⁰ C. This copolymer contains 96.6% by weight of ethylene and 3.2% of furfuryl octaciecenate.

Example 6

In a reactor as in Example 1, under nitrogen and

a temperature of 2O ⁰ C is maintained a mixture of benzene and n-heptane 1: 1.

is maintained at a temperature of 2O ⁰ C, is added 750 ml

In the 'iroj,! Funnel to the Jainfiairu ng d it polar monomers

gives ..iaii 50 Millii, ole vinylthiophene (J ^ _s jj Ch = CK ₂ V in one

aer Trcpftricuter for the catalytic system 3 millimoles Vanauin-triciiloric in 50 ml of a benzene-leptane mixture and in the other, 15 i.illimole diethylaluminum chloride in the eij; icn ^ c ucr called Miscnung.

- 12 -

109848/1775

BAD ORIGINAU

The nitrogen is turned off to the reactor and a mixture of ethylene and hydrogen is passed through the gas inlet pipe in a molar ratio of 3: 1 in a total of 140 normal liters per hour.

10 minutes after the start of the introduction of the gas mixture, the vinylthiophene and the catalysts are added at once. ί

Stopping the polymerization of 60 minutes after the start of the catalyst addition I mixture by adding 20 ml of ethanol for reaction j, the copolymer is separated from this mixture abound j it dries as described in Example 1. !

31.8 g of a crystalline copolymer of ethylene are obtained and vinylthiophene with a viscometric molecular weight of 109,000 and a sulfur content of 1.6% by weight.

Example 7

In a reactor as in Example 1, under nitrogen and

a temperature of 20 ⁰ C kept benzene and 25 millimoles vinylthiophene.

is kept at a temperature of 20 ⁰ C, are 750 ml

The nitrogen is turned off and a mixture of propylene and ethylene in the molar ratio P 2: '1 with a total amount of 99 normal liters per hour is introduced through the gas inlet pipe. 20 minutes after the start of the introduction of the gas mixture, its propylene: ethylene molar ratio is brought to 1: 1 and 2 millimoles of vanadium tetrachloride VCI4 in 60 ml of benzene and 16 millimoles of ethylaluminum sesquichloride 1/2 [Cl ₃ Al ₂ ( Add C ₂ Ii ₅ ) J in the same amount of benzene.

The catalysts are added in 30 minutes, the polymerization is stopped 40 minutes after the start of the catalyst addition by adding 30 ml of ethanol. Separation and The copolymer is dried as in Example 1.

- 13 109848/1775

29.5 g of a product are obtained which has the appearance of an unvulcanized elastomer. This ethylene / propylene / vinylthiopheri copolymer is amorphous under X-rays and has a viscometric molecular weight of 68 COO. Bs contains 48 * ethylene, 0.7% sulfur and 2.4 $ vinylthiophene.

Kach vulcanization under the same conditions as in Example 4 the vulcanized copolymer has the following mechanical properties:

tensile strenght 195 kg / cm ² i
i Expansion when tearing 440 % I.
i Modulus of elasticity at 300% expansion 120 kg / cm ₂ I.
! Shore hardness A 67 J
j Rebound 65% t
I.
I. Example 8

repeats the procedure of Example 7, but replaces the vinylthiophene with the adduct of vinylthiophene and cyclopentadiene

(CUD)

Benzene by a mixture of benzene and n-lieptane 1: 1, works at ⁰ ° C. and uses 2 millimoles of vanadium trichloride and 10 millimoles of diethylaluminum chloride, each dissolved in 60 ml of benzene, as catalysts.

56 g of a copolymer of ethylene, propylene and the adduct are obtained, which is like a non-vulcanized elastomer looks like. This copolymer is amorphous under X-rays and contains 0.75 sulfur.

After vulcanization, as in Example 4, the vulcanized Copolynere the following mechanical properties:

- 14 10984 & / 1775

BAD ORiOiNAU

tensile strenght 200 kg / cm ² Expansion when tearing 390% Modulus of elasticity at 300% expansion 130 kg / cin Shore hardness A 63 Rebound 651 Example 9

The procedure is as in Example 7, the propylene is replaced by i butene-1 and vinylthiophene with 50 millimoles of vinylfuran.

During the saturation phase, the molar ratio of butene: j

; Ethylene 3: 1, during the reaction phase 2: 1, the other working!

conditions are the same as in example 7.

; 18 g of a solid product are obtained which, like a non-

vulcanized elastomer looks like. This ethylene / butene-1 / vinylfuran copolymer is amorphous under X-rays. It has a viscometric molecular weight of 130,000 and a content of 37% ethylene and 2.3 l vinylfuran.

Example 10

A reactor is used as in Example 1, but which has an additional dropping funnel for introducing a dienic monoaceric. The reactor is located in a thermostatically controlled bath and is kept at 20 ^° C. *

The dropping funnel above the reactor are flushed with nitrogen. 25 Minimum dicyclopentadiene in 60 ml of benzene are added to the dropping funnel for introducing the dienic monomer. ; 25 millimoles of vinylthiophene in 60 ml of benzene are added to the dropping funnel for introducing the polar monomer. _{Two millittoles of VCl 4} in 60 nl of benzene are placed in one of the dropping funnels for introducing the catalytic system, and 16 millittoles of ethylaluene isesquichloride in the same amount of benzene in the other.

- $ 15 109 848 / $ 177

BATH ORIGINAL

750 ml of benzene are added to the nitrogen-filled reactor. The nitrogen is turned off and a mixture of propylene and ethylene in a molar ratio of 2: 1 in a total of 100 normal liters each is passed through the gas inlet pipe Hour one. After 20 minutes of introduction, the propylene: ethylene molar ratio is brought to 1: 1 and this is added dropwise Diene, the polar monomer and the catalysts. The addition is complete in 30 minutes.

The polymerization is stopped after 40 minutes by adding 30 ml of ethanol. The copolymer is separated off and dried as in Example 1.

26 g of a product with the appearance of an unvulcanized elastomer are obtained. This copolymer of ethylene / Propylene / dicyclopentadiene / vinylthiophene contains 50 wt. * Ethylene and 2.4 * vinylthiophene; its content of non-aromatic Double bonds, determined by determining the iodine number, are 5.2 per 1000 carbon atoms.

Vulcanization:

100 parts by weight of the copolymer obtained are mixed in a roller mixer with 50 parts of carbon black HAF, 5 parts of zinc oxide, 2 parts of sulfur, 1 part of mercaptobenzothiazole and 2 parts of tetraethylthiuram disulfide.

^{The mixture is heated to 160 °} C. for one hour in a press.

Properties of the vulcanized product: Tensile strength 150 kg / an ²

> Expansion at tearing 320 *

Modulus of elasticity at 300 * extension 130 kg / cm ²

1098A8 / 1776

Claims (21)

• ^ • ™ S!; I! 2? . ^Οίρ ' ^oec *> ^vbh DIETRICH LEWINSKY ^A n May 1971 PATENT ADVOCATE
SMfechM21 - Gofiha ^ str. 81 Telephone »17« 2 Soci ^ te Nationale des p £ troles d'Aquitaine, Courbevoie, (France) Patent claims: Process for the preparation of copolymers of olefins or of olefins and non-conjugated dienes with unsaturated derivatives of furan and / or thiophene in the presence of a catalytic coordination system, formed by combining an organometallic compound of one or more elements of I., II. Or III. Group of the periodic table of the elements with a compound of a transition metal of groups IV to VIII of this system, characterized in that one or more olefins and optionally one or more non-conjugated dienes are combined with one or more compounds of the formula in the presence of said catalyst in which X denotes oxygen or sulfur, ρ = 0 or and R ₁ , if ρ * is ο, is a vinyl radical or - (CIi ₉ ) -! represents, m is an integer between 0 and 12, and when ρ * is 1, represents an alkenyl radical having 2 to 20 carbon atoms, wherein the heterocycle can also be substituted one, two or three times with alkylene, arylene, cycloalkylene, Alkoxy, aryloxy, dialkylamino with 1 to 16 carbon atoms or with halogens. 2. The method according to claim 1, characterized in that the olefins are alpha-olefins of the formula R-Qi = CU ₂ , in which R 10984 8/1775 BAD ORfGiNAt Hydrogen, or an alkyl, alkylaryl having 1 to 16 carbon atoms can be. 3. The method according to claim 2, characterized in that the Alpha olefins are ethylene, propylene and butene-1. 4. The method according to claim 3, characterized in that the Alpha-olefins mixtures of ethylene and propylene or from, are ethylene and butene-1 to which non-conjugated dienes are added. 5. The method according to claim 4, characterized in that the non-conjugated diene are dicyclopentadiene, 1,5-cyclooctadiene, 1,4-hexadiene and the 5-alkylidene-2-norbornenes. 6. The method according to any one of the preceding claims, characterized in that the polar monomer vinyl furan, vinyl thiophene and is adducts of cyclopentadiene with vinyl furan or vinyl thiophene. 7. The method according to any one of claims 1 to 5, characterized i indicates that the polar monomer is an ester of an unsaturated carboxylic acid having 10 to 20 carbon atoms. 8. The method according to claim 1, characterized in that the catalyst system consists of an organoaluminum compound, which can also be halogenated, and a titanium halide or a halide or an oxyhalide of vanadium. 9. The method according to claim 8, characterized in that the compound of the transition metal in the form of a complex with an organic ligand is used. 10. The method according to claim 1, characterized in that the polar monomers in the reaction mixture in the form of a complex - 3 -109848 / 177S is present with a Lewis acid. * 11. The method according to claim 1, characterized gekennzeiclmet that the copolymerization at temperatures between -80 and +110 ⁰ C is carried out. 12. "The method according to claim 11, characterized in that the copolymerization Lei a terr.peratur between -30 and +60 ⁰ C is carried out. 13, Substantially linear high molecular weight copolymer consisting of non-polar units of one or more, alpha-olefins of the formula R-CH = CH ₂ , in which R is hydrogen or alkyl, aryl or alkylaryl with 1 to 16 carbon atoms, and optionally non-conjugated Serve and polar units of a compound of the formula 109848/1775 BATH ORIGINAL R ₁ - (COC) ~ * X in which X denotes oxygen or sulfur, ρ = O or 1, R ₁ , when ρ = 0, is a vinyl radical or - (CIi ₂ ), represents and m is an integer between 0 and 12, and, < if ρ = 1, an alkenyl radical with 2 to 20 carbon atoms ^: material represents atoms, the Ileterocycle also, Can also be substituted with halogens, alkylene, arylene, i Cycloalkylene, alkoxy, dialkylamino with 1 to 16 carbons | material atoms. 14. Copolymer according to claim 13, characterized in that it 99.9 to 75% by weight of non-polar units containing up to j 201 can come from non-conjugated dienes, and to 0.1 to 25 I consists of polar units. i 15. Copolymer according to claim 13 or 14, characterized in that that the polar units of vinylfuran, vinyltliiophene or from derivatives of these with cyclopentadiene. 1G. Copolymer according to Claim 13 or 14, characterized in that the polar units are furan or thiophene esters a linear unsaturated carboxylic acid having 10 to 20 carbon atoms. 17. Copolymer according to claim 13 or 14, characterized in that - that the non]; olar units of a single olefin, such as ethylene, propylene or Hütten-1 originate. 18. Copolymer according to claim 13, 14, 15 or 16, characterized in that the non-polar units are derived from ethylene and propylene or from ethylene and lutene-1, the proportion of units from propylene or from butene-1 being between 5 and 75 wt . ο of the copolymer and the content of ethylene is at most 75 wt.% of the copolymer is. 19. Copolymer according to claim 13, 14, 15 or 16, characterized in that that the non-polar units are derived from ethylene, propylene and a non-conjugated diene, where the ethylene content in copolymers does not exceed 75%, the total propylene and diene content between 5 and 75% and the diene content is between 0.1 and 20% by weight. 20. Copolymer according to claim 19, characterized in that the non-conjugated diene is 1 _t 4-hexadiene, dicyclopentadiene, 1,5-cyclooctadiene or 5-alkylidene-2-norbornene, the alkylidene radicals of which have 1 to 4 carbon atoms. 21. Elastomer, characterized in that it is obtained by vulcanization of copolymers according to Claim 18, 19 or 20. 109848/1775
BATH ORIGINAL