DE1645405A1 - Vulcanizable copolymers of olefins and process for their preparation - Google Patents

Description

"Vulcanizable copolymers of olefins and processes for their production"

Priority: November 22, 1966, Japan, No. 76822/66

The invention relates to vulcanizable copolymers of ethylene and / or C1-olefins with bicyclic hydrocarbons and a method for their production.

Attempts have long been known, for example amorphous, saturated hydrocarbon polymers vulcanizable with sulfur or phenolic resins by introducing double bonds, for example the production of butyl rubber, which is made by interpolymerizing isobutylene with small amounts of isoprene.

009821/1756

ORlGiNAL !, NSPS

Recently, due to the discovery of the Ziegler catalysts found a process for the production of amorphous copolymers from ethylene and propylene. Since dleoe Miochpolyinerisate are excellent elastomers due to various properties, a lot of attention was paid inside » In these olefin polymerizates, therefore, was also tries to vulcanize amorphous copolymers with sulfur or phenolic resins by introducing various diene compounds, similar to butyl rubber. However, it is not always possible to predict that "a certain diene compound or a certain polymerization process to give rubbers with excellent vulcanization properties will lead.

From British Patent No. 880 904 which describes a method for the production of copolymers of aliphatic monoolefins and unsaturated bicyclic hydrocarbon compounds describes the use of e.g. Horbornadien and dicyclopentadiene as unsaturated derivatives of bicyclo- (2,2,1) -heptane known here as a catalyst system Catalyst with an active surface described, which is composed of the mixture of a compound of a heavy metal of IV. To VII. Subgroup or the VIII. Group of the Periodic Table and either (a) an organic compound of metals from I.-to IV. Group, preferably II. To III. Group of the Periodic Table or (b) a wetallhydride or an organometallic hydride or (c) an organic metal halide compound.

00982 1/1 7 SS ^ßAD original

A typical example of this catalyst is one that by reacting a Trialkylaluiainiuiaverbverbindungen with ana Tetrahalide of titanium or vanadium was obtained. For example The British patent uses a triisobutylaluminium and vanadium tetrahalide catalyst.

K. Gladding and co-workers £ ""! <. and EG Prod. Res. Dev «1.

65 (1962) _- 7 'found on the basis of detailed investigations of ternary ethylene-propylene-diene copolymers which were produced using tetrachlorethylene as a solvent in the form of triisobutylaluminum-vanadium trichloride as a catalyst that the use of aliphatic short-chain Serving is not advantageous, since this inhibits the polymerization extremely; Conjugated dienes are likewise undesirable. The preferred dienes are dicyclopentadiene, methylene norbomene, methyl norboronadiene and II-ethyl-III-tridecadiene.

Patent specifications that go back to the above-mentioned literature, e.g. British Patent 925,468, describes the following unsaturated norbornene derivatives as cyclic dienes

GH = CH-Q '

CH-Y * CH ₂ -C-GH ₂ Y

CH-C-CH ₂ -Y

009821/17 56

BATH ORIGINAL

R "

in which R "means a hydrocarbon3t with 1-8 C-atoms', copolymerized

The vinyl norbornene compounds which can be used according to the invention are surprisingly easy to copolymerize with olefins such as ethylene and propylene. As copolymerized isopropenylnorbornene z.ß _o much faster than methyltetrahydroindene, an isomer which is obtained by Diels-Alder reaction of cyclopentadione and isoprene.

wherein X ¹ , X ", Y ^f , R and Q ¹ denote alkyl radicals and Ϊ denote an alkyl radical or an Y / hydrogen atom. The above-mentioned liorbornene derivatives have either a terminal vinyl group or a medium double bond (vinylene group).

In addition, several "methods of making with ί Using sulfur vulcanizable olefin copolymers of norborae compounds known which have unsaturated groups wear in the side chain; See e.g. British Patents 1,018,778 and 1,007,908. The double bonds in the side chains however, these compounds are not double bonds of the vinylidene type "

It has now been found that vulcanizable copolymers are produced Can be grounded if ethylene and / or Λ-olefins are used with vinyl norbornene compounds of the formula

009821 / 17S6

BATH ORIGINAL

This not only makes it possible to use the copolymer in a short time .Reaction time, but also the concentration of the Isopropenyl norbornene in the polymerization system can be reduced "Likewise important is the fact that in a stage a extremely high conversion can be achieved. Also owns the received Mixed polymer with remarkably good vulcanization properties.

Jis is well known that during the sulfur vulcanization e.g. a terpolymer of a diene and ethylene and propylene in general can only be vulcanized very slowly. Therefore, connections are with a high rate of vulcanization is desirable. The vinyl norbonene compounds which are used in the inventive jj Methods used are characterized in that they have side chains of the vinylidene type and are excellent in rubbers Give vulcanization speeds "e.g. they vulcanize 3-4 times faster than a terpolymer, in which Dicyclopentadiene was used as the diene.

It cannot be predicted that the interpolymerization of olefins with the basket nucleus compounds used according to the invention using any of the catalysts gives excellent interpolymers. It was found that copolymers are used having excellent vulcanizing properties when an ICatalyst is used which as components an organoaluminum halide of the general formula

009821 / 1788- ^BA ° ^0RIStNAL

in which R is a hydrocarbon atom with 1-20 carbon atoms, X is a halogen atom and η is a number from 1 to 2, and contains a vanadium compound in which the vanadiura atom is bonded to a halogenated, acetylacetonate, alkoxy, cyclopentadienyl or an organic acid radical is. Therefore, the present invention relates to a process for preparing vulkanisierbareii copolymers of olefins, which is characterized in that _t in the presence of a Katalysatorsy3temo

which contains a vanadium compound of the type described above and an organoaluminium halide of the general Fonael ^ 1R X, as an effective component, ethylene and / or ^ -olefins of the general formula CH ₂ -CIIR ', in which R ^{1 has} the above meaning, with a Vinyl norbornene of the general formula

in which R "has the preceding meaning, copolymerized o

Specific examples of (^ - olefins of the general formula CH ₂ = CHR ', in which R * is an alkyl group with 1-8 carbon atoms and propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, heptene -1, octene-1, nonene-1, decene-1, 5-methylnonene-1, 5,5-dimethyloctene-1, 4-methylhexene-1, 4-methylheptene-1, 6-methylheptene-1 and 5 »6 _# 6-'J? Rimethylhepten-le Excellent results are obtained in particular when ethylene and propylene or butene-1 are used as olefins .

BATH ORIGINAL

009821/1756

Special examples for vinyl norbomene of the general formula mentioned, in which H "is an alkyl, aryl, aralkyl, alkylaryl or cycloflkyl radical with 1-8 carbon atoms, are 5-Iaoproponyl ~ 2-norl) and the like, 5 - (l'-ethyl-vinyl) * - 2 ~ norbornene, 5 ~ (1'-n-propyl-vinyl) -2-nortoo.riien, 5- (1 * -isopropyl-vinyl) -2 ~ norbornene, 5 - (1 '-n-Butyl-vinyl) -2-norbornene _t 5- (1' -n-Hcxyl-vinyl) ~ 2 ~ norl) or ~ nen, S-Cl'-Cyclohexyl-vinyiy ^ -norborncnj 5- (l ^f -phenyl-vinyl) -2 ~ norbornene and 5-

In particular there are compounds having alkyl groups of 1-4 carbon atoms very favorable results.

The organoaluminium halides of the general formula AlR _n X ^ _n are those in which each R is a hydrocarbon radical with 1-20 carbon atoms, X is a halogen atom and η is a number from 1 to 2. Preferred compounds are those in which H is an alkyl, aryl, aralkyl, alkylaryl, or cycloalkyl group. In particular, alkyl compounds having 1-6 carbon atoms give favorable results. Ea can also use compounds with other hydrocarbon groups, e.g. cyclopentadionyl or alkenyl groups. In the formula, X denotes chlorine, bromine or iodine, in some cases also fluoro. It is not necessary that the organoaluminum halide is a single compound Mixtures of different compounds which fall under the general formula Averden can also be used. In the process of the present invention, mixtures of dialkylaluminum halides or alkylaluminum dihalides, mixtures of irialkylaluminum compounds and alkylaluminum halides, or aluminum trihalide halides and binaural aluminum trihalide halides, can also be used in particular.

BATH 009821/1758 ■

In the present method, in particular, excellent Results obtained using organoaluminium halides which are substituted with ethyl groups. These organoaluminum halides are e.g. ethylaluminum dichloride, Ethylaluminum dibroaid, ethy1aluminium diiodide, n-propylalurainlum dichloride Isobutylaluminium dichloride, n-hexylaluminum dichloride, Octadecyl aluminum dichloride, phenyl aluminum dichloride, ethyl aluminum sesquichloride, Ethylaluminum seoquibroiaid, Äthylalur.iiniumsesquijodid, Methylaluminium sesquichloride, n ~ propylalurainium3e3quichlorid, Isobutylalurainium sesqui-chloride, n-hexylalu— mini sesquichiride, cyclohexyl aluminum sesquichloride, 2-ethylhexyl aluminum sesquichloride, Laurylalurainiuaisesquichlorid, Diethylaluminumchlorid, · Dimethyl aluminum chloride, di-n-butyl aluminum chloride, Ethyl propenyl aluminum chloride, dicyclopentadienyl aluminum chloride and cyclohexylethylaluminum chloride, mixtures of these compounds in various proportions, Mixtures of the same with trialkylaluminum compounds or aluminum halides, and mixtures of trialkylaluminum compounds with aluminum halides, which then have the general formula AIR X ^ correspond.

Vanadium compounds, which act as the other component of the catalyst are used in the process according to the invention, contain at least one halogen atom, or an acetylacetonate, Alkoxy, cyclopentadienyl or an organic acid group bound to the vanadium atom. Such connections are, for example. Vanadium halides, vanadyl halides, vanadium acetylacetonate, Vanadyl acetylacetonate, vanadium haloacetylacetonate, vanadyl

009821/1758

haloacetylacetonates, orthovanadates, for example those containing hydrocarbon groups with 1-20 carbon atoms, in particular those containing alkyl groups with 1-8 carbon atoms, vanadyl haloalkoxides, cyclopentadienylvanadiuni, halocyclopentadisnylvanadium and vanadium salts of organic acids. Specific examples of such compounds are vanadium tetrachloride, Vanadiuiatriehlorid, Yanadyltrichlorid, vanadium triacetylacetonate, Yanadyldiacetylaeetonat, Dichlorvanadylacetylacetonat, Chlorvanadylacetylacetonat, tCriäthylorthovanadat, Triisobutylorthovanadat, tri-n-hexylorthovanadat, l'ricyclohexylorthovanadat, Triphenylorthovanadat, Chlorvanadyldiäthoxyd, Bronvanaäyldiäthoxyd, Chlorvanadyl-di-n-octoxyd, Dichlorvanadylinethoxyd, Dichlorvanadylethoxide, Dichlorvanadylstearoxyd, Dieyclopentadienylvanadium, Vanadium acetate and Vanadium propionate · In the process according to the invention, the polymerization is carried out with catalyst systems which contain organoaluminum halides and vanadium compounds of the aforementioned type as effective components. However, certain compounds can also be added to the catalyst as a third component. These are, for example, electron donors, which can enter into addition compounds or other reactions or interactions with the organoaluminum halides or the vanadium compounds. JÜ3! Tons various oxidizing agents are added which prevent the vanadium compounds are reduced by the organoaluminum and deactivated. Examples of electron donors are amines, cyclic nitrogen-containing compounds, acid amides, ethers, eater, ketones, aldehydes and compounds of Kiementen of the Vb group deo Periodenoyutcma such as phosphorus, aromas, antimony and Wiamut _e

BATH

009821/1756

Examples of oxidizing agents are halogens, metal halides, oxygen, nitro compounds, nitroso compounds, organic compounds Hit rates, nitrites, Ιί-oxides, P-oxides, azo compounds, organic © Sulfides, disulfides, quinones and acid halides.

When carrying out the method according to the invention, there is Amount ratio of organoaluminum halide to vanadium compound not limited to certain values, but favorable results are obtained if the two components in the ratio f nis lsi to 1000; l, preferably 2; i to 300si, can be used. The vanadium compound is used in a concentration of 0.001 to 30 mmol / liter of reaction medium, in particular 0.01 to 2 inMol / Liters and the organoaluminum halide in one concentration from 0.1 to 100 mmol / liter, in particular 0.5 to 20 mmol / liter, used.

When the organoaluminum compound is a trialkylaluminum compound is used as the catalyst component is the polymerization activity generally low. But even if the activity is the same as when using an organoalurainium halide is achieved, the polymer obtained is less valuable in its properties. There are, for example, numerous cases in which a relatively large amount of crystalline components form or the diene component reacts poorly, so that obtained product does not have sufficiently good vulcanization properties.

009821/1756

In contrast, those according to the present process obtained copolymers various good properties; E.g. they are of excellent homogeneity in comparison those obtained by the usual methods. Vullcanizates made from such copolymers are therefore also excellent physical properties, and vulcanizates with high tensile strength are obtained «

Particularly high polymerization activity can then be achieved when the organoaluminum halides used are mixtures of dialkyl aluminum halides and ivlonoalkylalurainium dihalides are. Copolymers, which when using such catalyst systems obtained v / ground, have particularly good vulcanization properties. Organoaluminum halides, which are represented by ethylene groups are substituted, give particularly advantageous results. In practicing the present method can add the catalyst components to the reaction system can be fed in different ways. E.g. you can see the catalyst components and then these Mixture in the reaction vessel, which contains the monomers, enter, or the catalyst components are individually the Reaction oystera added If you want a high catalyst activity achieve, it is preferred to mix the organoaluminum halide with the vanadium compound in the presence of the monomers. The polymerization is also at the lowest possible temperature to delay the decrease in the activity of the catalyst system which occurs over time.

009821/1756

On the basis of thorough investigations into the catalyst systems which are suitable for the production of the copolymers according to the invention, it was found that the catalyst system described below is particularly suitable. According to this preferred embodiment, the invention relates to a process for the preparation of copolymers, which is characterized in that ethylene and / or mono-olefin of the general formula CIL ^ CHR *} in which R ^{r has} the above meaning, and a vinyl norbornene of the general formula

R! ¹

in which H "has the above meaning, in the presence of an organoaluminum dihalide of the general formula AlRX ₂ * in which R is a hydrocarbon radical having 1-20 carbon atoms and X is a halogen atom, and a sulfur compound of the general formula

R ^IY SO _m Y
IV

in which R is a hydrocarbon radical with 1 * 20 carbon atoms or is a derivative thereof and Y is a halogenator and m is the Number 1 or 2 and a vanadium compound in which the vanadium is attached to at least one halogen atom or an acetylacetonate, Alkoxyd, cyclopentadienyl or an organic acid residue is bound, is copolymerized

009821/1756 ^ _{0 0RIGiNAL}

16454Ό5

This catalyst system combination has several excellent ones Properties. First and foremost, the vanadium compound can be used in a smaller amount compared to other, hitherto customary catalyst systems be applied. For example, if a previously common catalyst system, the vanadium component in a Concentration of 0.1 to l_mMol / liiter required, with one Catalyst according to the invention the same effect can be achieved in a concentration of e.g. 0.001 to 0.1 mol / liter. In this way, not only the catalyst costs can be reduced, but also the catalyst parts remaining in the polymer can also be removed more easily and completely.

This advantage can only be achieved with simultaneous use of the

IV gel compound of the general formula R SO X achieves v / grounding · The use of this sulfur compound results in dife polymerization greatly accelerated. It is believed that this sulfur compound is a complex or an addition compound with the organoaluminum dihalide, which is an active form of the catalyst. This is extremely surprising mainly because it had previously been assumed that sulfur compounds inhibit catalysts from Ziegler- " Act type.

Another excellent property of the catalyst system according to the invention is the fact that the sulfur compound influences and co-determines the molecular weight of the product. In the Olofinpolymerioation with Ziogler catalysts, the polymers obtained are often of extremely high molecular weight and the control of the molecular weights here is

not an easy problem. ,

ι.

009121/1758

When using the catalyst system according to the invention can the molecular weight of the interpolymer can be kept lower by increasing the amount of the sulfur compound.

IV The sulfur compounds of the general formula H SO Y aind the sulfonic acid and sulfinic acid halides. Here the halogen is either chlorine, bromine or iodine, in some cases it can

IV
also be j? luor, and R is a hydrocarbon radical, which can also be substituted by inert groups. Specific examples of these compounds are benzenesulfonyl chloride, benzene

sulfinyl chloride, benzenesulfonyl bromide, benzenesulfonyl iodide, p-toluenesulfonyl chloride, o-toluenesulfonyl chloride, m-xylenesulfonyl chloride- (4) »benzylsulf, onyl chloride, it-naphthylsulfonyl chloride, p-chlorobenzenesulfonol, p-chlorobenzenesulfonola, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, m-xylenesulfonyl chloride . 2-aminotoluenesulphonylchloride- (4) ι 4-aminophenolsulphonylchloride, ß-liaphthylamine-ilj-sulphonylchloride- (5) t naphthol- (2) -disulphonylchloride- (3f6), 1,2-dioxyanthraquinonesulphonylchloride- (7) »cyclohexanesulphonylchloride- (7)» cyclohexanesulphonylchloride Propanesulfonyl chloride, athanesulfonyl chloride, chloroethanesulfonyl chloride and methanesulfonyl chloride. Other compounds with the groups mentioned above can also be used. will.

In practicing the method according to the invention it is generally advantageous to use the organoaluminum halogen compounds in a concentration in the reaction mixture more than 0.1 mmol / liter, in particular from 1 to 20 ml / liter

»Use 4 ·,;

Higher concentrations can also be used. Bio

IV promote sulfur compounds of the general formula E SOJ the polymerization reaction, even if it is proportionate small amounts are present; therefore, it is not advantageous to use too large an amount. In general, the Sulfur compounds are used in an amount of 0.001 to 10 moles per mole of the organoaluminum halide compound. The best Results are obtained when approximately equimolar amounts are used The vanadium compound, i.e. the third component of the Catalyst system, causes an increase in the polymerization activity even in the smallest amounts. In the presence of I £ close a.ß. in the range of 0.000001 to 0.001 mmol / liter of reaction mixture, excellent reaction activity is achieved. This is a property that was previously used, for example, in Ziegler catalytic converters using titanium compounds has not yet been observed. This is a particular advantage of the present one Invention. The preferred concentration range is 0.001 to 2 mHol / liter, but a higher concentration can also be used. concentration e.g. from 2 to 10 mHol / liter can be used «In general, the vanadium compound is used in an amount of OtOOOOl to 1 mliol per mole of the organoaluminum compound used 'if this is in the form of an organoaluminum halogen compound is present. The polymerization activity, however, also depends on the nature of the monomers and their composition, therefore the optimal concentration depends on these conditions *

00.9821 / 1750

When preparing the catalyst, it is not necessary to follow a specific sequence for adding the individual components to be observed. The catalyst activity is, however, in generally higher when the components of the catalyst system of the reaction mixture are mixed individually and not premixed are fed. The better results are achieved

IV Y / enn the sulfur compound of the general formula R SO Y is first mixed together with the organoaluminum halogen compound «This way of working is better than if the 7-

TV

bond R SO Y is previously mixed with the vanadium compound «, In the method according to the invention, the vinyl norbomene can be used to carry out the polymerization reaction from the outset in the reaction mixture be dissolved, but it can also be fed together with the other monomers, which is continuous or can be done discontinuously. The vinyl norbom is common in a concentration of about 1 to 1Ό mmol / liter in the

liquid reaction mixture used. If the portion of the service j in the copolymer produced an Ood number of 1-50, j preferably corresponds to 3 * 20, an excellent vulcanizate can be obtained.

In accordance with the present invention, Icsnn when implemented A vulcanizable copolymer can already be obtained from ethylene alone with the diene. However, JSs is beneficial in order to obtain an amorphous, elastomeric copolymer, to carry out the reaction together with an ÖC-01efin, so as to to obtain a terpolymer. Production is particularly preferred of terpolymers from 40 - 90 mol .- # ethylene, 10-60 mol .-% of the C-OIefin, and 0.5 to 10 mol .- # of the vinyl norbornene compound.

009821/1756

The use of propylene or butene-1 is particularly preferred as oC'-olefin and isopropenylnorbornene as vinylnorbornene compound.

Be used in the practice of the method may be selected depending on the reaction conditions of the cheapest polymerization "Iia general the pressure is between 1 to 30 kg / cm ο The polymerization can also be carried out at reduced pressure. An inert gas can also be present in the reaction mixture; this depends on the other conditions »

Ms reaction temperatures can be up to about +100 ⁰ C in the range of about -78 ⁰ C. In general, a temperature range from -55 to + 7O ⁰ O gives very good results. The polymerization temperature should be brought as the optimum temperature in accordance with the particular catalyst used and it is advisable to coordinate the catalyst activity and its decrease with the reaction time accordingly.

In general, when carrying out the invention Process an inert solvent is used. The Binediura reaction can also be a liquefied monomer. As suitable Solvents generally serve hydrocarbons or halogenated hydrocarbons. Examples are propane, Butane, pentane, hexane, heptane, octane, petroleum ether, ligroin, other petroleum fractions, benzene, toluene, xylene, cyclohexane, methylcyelohexane, jVlethylendi chloride, ethylene dichloride, triehlorethane, Tetrachlorethylene, butyl chloride, chlorobenzene and bromobenzene.

009821/1758 '. 'j

liach completion of Polyraerisationsreaktion Hach ~ treatment is carried out in a usual manner, the obtained mixed polymer au purify and isolate Usually is carried out post-treatment with alcohol _s water vapor or alcohol-hydrochloric acid, alkali, aqueous emulsions or anderoiMethoden as in the polymerization by means of Ziegler-Natta-Kata3, ysators are common *

The polymerization product can also be precipitated, without previously being subjected to any of the above-mentioned aftertreatments, or it just becomes the solvent removed * whereby the originally dissolved product is isolated and recovered. In addition, it is also is% borrowed during or after this treatment the product antioxidant or to mix in other additives.

The invention is illustrated in more detail by the examples.

example 1

1 liter of approved n-heptane "was filled with nitrogen in a th 2-liter four-necked flask and warmed to 25 ° C in the thermostat.

An ethylene-propylene gas mixture with an ethylene content of 30 mol .- # was added at a rate of 3 liters / min to introduced to saturate the solvent. 6 mmol of 5-isopropenyl-2-norbornene were added to this mixture, then

2 mmoles of ethyl aluminum eesqui chloride and 0.25 mmoles of vanadium trichloride added in heptane. After 15 minutes, the

009821/1756 |

Completion of the reaction containing 20 ml of ß-phonylnaphthylamine » Methanol added.

The reaction mixture was made sufficient with methanolic hydrochloric acid washed, after further washing several times with a tap the copolymer was precipitated with methanol, washed and dried. 11.35 g of a white, amorphous copolymer were obtained obtain. The copolymer had a proportion of 31.8 mol. S ^ propylene and an iodine number of 11.8; ee was in n-heptane Completely soluble at room temperature.

50 parts of HAF carbon black, 5 parts of zinc oxide, 1.5 parts of sulfur, 1.0 part of stearic acid, 0.5 part of liercaptobenzothiazole and 1.5 parts of tetramethylthiuram monosulfide were added to 100 parts of the copolymer and mixed on the roller. The mixture was ^{pressure vulcanized at 160 0} O for 40 min »

The tensile strength of the vulcanized product was 238 kg / cm (tensile strength meter according to Schopper). The modulus of elasticity 500 fi was 218 kg / cm ² , the elongation was 390 #.

Example 2

According to Example 1 1 liter of n-heptane was saturated with ethylene having an ethylene content of 27 PropylenrGsfsgemisch Kol .- # at 25 ⁰ C. 5 mmol of 5-isopropenyl-2-norbornene were added to this. This mixture was admixed with 3 mmol of diethylaluminum chloride and 1 mmol of vanadium triacetylacetonate. The duration of the polymerization was 15 minutes, the ethylene-propylene gas mixture being introduced and the procedure being carried out under the conditions of Example 1 ο

009821/1756

Eb were 13 "11 g soluble in heptane copolymer receive this Terpolyraer had a propylene content of 52.9 MoI ₀ -Jo and the iodine value was 7.3.

Example 3

Example 2 was repeated, but using triethyl orthovanadate instead of j of vanadium triacetylacetonate as the catalyst. The polymerization was carried out within 10 minutes with an ethylene-propylene gas mixture which contained> 32 mol. Ea \ 10.04 g of mixed polymer were obtained «

Example 4

Example 1 was used. The gas mixture consisted of ethylene and butene-1, the ethylene content being 30 mol.-y *. 1 liter of tetrachlorethylene? <Narde at 60 ⁰ C with the gas mixture saturated. 5 mmol of 5- (l'-ethyl-vinyl) -2-norbornene were added as diene. 10 miviol of an organo-aluminum halide solution prepared by mixing triisobutyl aluminum and aluminum bromide in a ratio of 1: 1 was added. Finally 4 mmoles of vanadium tetrachloride were added. The polymerization time was 1 hour. 3 # 72 g of terpolymer were obtained.

example 5

1 liter of n-IIeptane was placed in a 2 liter four-necked flask introduced and the flask kept under Stielest off atmosphere. The heptane was saturated with a gas mixture of 35 mol .- # ethylene and 65 mol .- ^ propylene at 25 °. Thereupon 6 elMoI Isopropenylnorbornene, 10 mmol ethylaluminum dichloride, 10 Benzol sulfonyl chloride and 0.0 imMoI vanadyl trichloride in the

009821/1756

BATH ORIGINAL

mentioned order fed. The polymerization was carried out over a period of 30 minutes, the gas mixture being introduced. The polymerization was then terminated by adding 15 ml of a methanol solution of β-phenylnaphthylamine. The polymerization product dissolved in the heptane was washed several times with a mixture of methanol and hydrochloric acid in a ratio of 1: 1 and then washed several times with V / aaser. The purified solution was poured into a large excess of methanol to precipitate the copolymer. No polymer insoluble in heptane was obtained in this procedure. The product obtained was dried in vacuum at 4O ⁰ · G were 10.18 g copolymer with a Intrin-

aio viscosity of 1.55 dl / g with a propylene content of 25.2 mol · -? δ and an iodine number of 14.7. This polymer nsprodukt ο as in Example 1, vulcanized with sulfur and the vulcanization product had a tensile strength of 205 kg / cm ² at an elongation of 300% and a 300 i> elasticity

2
module of 192 kg / cm.

If the example is repeated with the modification that Benzolsulf ochloride was omitted, the yield achieved was only 0.02 g under the same working conditions.

Beis piel 6

Using the same working method as in Example 5, 4 mmoles of ethylaluminum dichloride, 2 mmoles of p-toluenesulfonyl chloride, 0.02 mmoles of triethyl-o-vanadate and 6 mmoles of isopropenylnorbornene in 1 liter of cyclohexane dissolved.

009821/1758

The polymerization was performed within 30 min at 20 ⁰ C, ■ wherein a Gasinischung from 30 Mol ethylene 56 and 70 Mpl ₈ - pylene was introduced% product I. Eb 12.95 g of mixed polymer were obtained _e j

Example 7

Eei the same procedure as in Example 5 , the polymorization reaction using τοη 5 πΜοΙ methanesulfonyl chloride anateile of the benzenesulfonyl chloride and 0.05 mmol of vanadyl acetylacetonate dichloride and 5 mmol of isopropenylnorbornene instead of. VanadyItriChlorids carried out. 8.47 g of 2-polymer were obtained.

Example 8 . '·.

Using the working conditions of example Ϊ, Ethylene introduced into 1 liter of n-heptane until saturation.

To this solution, 1 mmole of 5 ~ (1 ^f -ethyl-vinyl) -norbornene-2.2 in moles of isobutylaluminum dichloride, 1 nHol of p ~ toluenesulfonyl chloride and 0.003 mmole of vanadiurate tetrachloride were added in this borrowing sequence. The duration of the polymerization was 10 minutes, with ethylene being passed in uninterruptedly. 8.91 g of a mixed polymer insoluble in heptane were obtained.

Θ09821 / 1756 BAD

Claims (1)

Claims le method for Herateilung of vulcanizable mixed poly ι merisates of olefins, characterized in that ethylene ι and / or ώ -olefins of the general formula CIL ^ CHR ¹ , in which j E ^{1 is} an alkylreat with 1-8 C atoms, with a urorbornene compound of the general formula in which R "is a hydrocarbon radical with 1-8 C atoms, in the presence of a catalyst system consisting of (a) an S ! Organoaluminum halogen compound of the general formula AIR X ,, j in which R is a hydrocarbon residue with 1-20 carbon atoms, X is a halogen atom and η is a number from 1 to 2, and (b) a Vana! dium compound which contains at least one halogen atom or one acetyl ·; ι acetonate, alkoxide, cyclopentadienyl or an organic j Carries acid residue on the vanadium atom, polymerizes _o ! 2. The method according to claim 1, characterized in that
Ethylene and propylene or ßuten-1 and isopropenylnorbornene
can be used as starting monoiaere. 3. The method according to claim 1 and 2, characterized in that
that the concentration of the organoaluminum halide is 0.1 to 100 mmol / 1, preferably 0.5 to 20 mmol / l and that of the vanadium ' Compound 0.001 to 50 mmol / 1, in particular 0.01 to 2 mmol / l ι is · Documents iAit7I1Abe.2Nr.1 Satz3desXnderuna9flA2. *. 2ila51 009821/1756 4 · Process for the production of vulcanizable mixed poly- j meren. of olefins, characterized by the fact that ethylene i and / or a cC-Qlef in the general formula CH ₂ = CHR ', in which R ^{1 is} an alkyl radical with 1-8 G atoms, with a Korbornenverbin- formation of the general formula; in which R "is a hydrocarbon radical with 1-8 carbon atoms, j I in the presence of a catalyst system from a) an organoalu | Minium halogen compound of the general formula AlRX ₂ 1 in which j R is a hydrocarbon radical having 1-20 carbon atoms and X is a halogen atom, b) a sulfur compound of the general j TV IV ' Formula R SO Y, in which R is a hydrocarbon radical with! m ' 1-20 carbon atoms, which can optionally be substituted, Y is a halogen atom and m is a number from 1 to 2 th, and c) a vanadium compound, which at least one ι Halogen atom or an acetylacetonate, alkoxy, cyclopentadienyl! or carries an organic acid residue on the vanadium atom, poly- merisierto ', - .. I 5o method according to claim 4 »characterized in that the j organoaluminium halogen compound of the general formula AlIlX ₂ j ethylaluminum dichloride, the sulfur compound of the general formula R SO Y! Üoluenesulfonyl chloride, benzenesulfonyl chloride,; Methanesulfonyl chloride or ethersulfonyl chloride, and the vanadium compound is a vanadium halide, vanadyl halide, vanadium, 009821/1756 aeetylaeetonat, Vanadiuinhalogenacetylaeetonat, Vanadylhalogenacetylacetonat, Orthovanadic acid ester or a halovanadyl alkoxide is. 6, process according to claim 4. ~ 5t characterized ₉ that the cC-olefin is propylene or butene-1 and the iiorbornenverbinaung isopropenylnorbornene «. , 7. The method according to claim 4-6, characterized in that the organoaluminum halide compound in a concentration of 0.1 to 100 mHol / l, in particular 0.5 to 20 sMol / l, and the vanadium compound in a concentration of .1 χ 10 to 10 inliol / l, in particular 0.0.01 to 2 ΐπϊίΐοΐ / ΐ, is used » 8o method according to claim 4-7 »characterized in that IV the sulfur compound of the general formula E SOJ in an amount of 0.001 to 10, in particular 0.1 to 2 mol per mol of the Organoaluminum halide is used. 9. The method according to claim 4-8, characterized in that the sulfur compound of the general formula RSO Y and the Organoaluminum halide are first mixed with one another, especially in equimolar proportions, and that this mixture is added to the heating mixture. 10. The method according to claim 1-9 »characterized in that the polymerization reaction is carried out at a pressure of less than 30 kg / cm and at a temperature in the range of -78 ° · to +100 ⁰ C · 009821/1756 11oHischpolymerisate from ethylene and / or an α-olefin of the formula CH ₂ = CIiE ', in which E ^{} is} a Cj ^ g-alkyl radical ₉ with a norbornene compound of the general formula - C = CH ₂
R » in which R "is a hydrocarbon radical with 1-8 carbon atoms ο 12 ο copolymers according to claim 6, consisting of ethylene = · and ecopylene, or butene-1 and isopropenylnorbornene units. 13 · A sulfur vulcanizable _y elastomeric copolymers according to claim 7, consisting of 40-90 fo ethylene-s $ 60-10 5 propylene and 0,5 - 10 # Isopropenylnorborneneinhoitono 00982 1/1756