DE2154635A1 - Catalyst system for the polymerization of unsaturated compounds, processes using the catalyst system and products obtained by the process - Google Patents

Description

BANK ACCOUNT:
BANK H. HOUSES

Case 432
97 / Si

SNAM PROGETTI S.p.A., Milan / Italy

Catalyst system for ei <.e polymerization of unsaturated compounds, processes using the catalyst system and products which are obtained after the process

The present invention "relates to a new catalyst system for the production of high molecular weight polymers starting from unsaturated compounds as well as the products of high molecular weight obtained with such a catalyst system.

The present invention also relates to a method which using the above catalyst system allows the use of higher reaction temperatures than the usual and which higher yields and the production of polymers with higher Molecular weight and generally better properties allows what is evident from the operating conditions chosen and depends on the other factors known to those skilled in the art.

209821/0900

The present invention therefore particularly relates to the use of catalyst systems which have a reducing aluminum compound, such as the dialkyl monohalide together with minor amounts, which are critical and generally minor, of a halogen, preferably iodine, or one

remove

Inter-halogen compound (for example, ICl, IBr, etc.) as cocatalyst / at temperatures z \ iischen 0 and 100 ⁰ C. The peculiarity of the invention, which differs greatly from the prior art is in the nature of the cocatalyst used.

The field of application of the present invention is very broad and includes, for example, the manufacture of butyl rubber, which showed a remarkable interest from an industrial point of view will.

It is known that butyl rubber using a copolymer! sat icne process and using cationic accelerators was manufactured industrially.

The copolymerization is carried out in particular using AlCl ;, in a ÄthylChlorid- or methylene chloride solution at -10o C ^0.

The use of a solid catalyst, which solvents in conventional hydrocarbon-containing insoluble and in a solvent of chlorine is slightly soluble, brings some difficulties in the effective control of such a reaction with them.

It must be pointed out that the preparation of a catalyst solution is quite complicated and by bubbling a stream of ethyl or methyl chloride through a catalyst bed, which consists of solid aluminum trichloride,

he follows.

The subsequent determination of the / catalyst concentration obtained by titration of the AlCl ₅ is also difficult and gives few reliable values.

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- j -

The Aiiinelderin has now surprisingly found that it it is possible to polymerize unsaturated compounds from industrially interesting products using a catalyst system, consisting of a reducing aluminum compound, such as an organo-metal aluminum halide and from a cocatalyst which is produced by reaction with the catalyst is capable of releasing cations. Said cocatalyst can be a halogen introduced as such or another internal be ogen connection.

The new catalyst system brings all the advantages of the above-mentioned catalyst systems with it, combined with a loading remarkable ease of control of the polymerization reaction due to the solubility of said catalysts in the usual organic solvents. If necessary, it is also possible to work with very small amounts of solvent and even without solvent at all, with the unreacted Monomers themselves behave like a solvent.

Furthermore, compared to the last-mentioned system, this new catalyst system has the advantage at higher temperatures To deliver products with the same T-iolekulai weight.

Furthermore, the catalyst system according to the invention allows a comparison to the Brönsted acids - also during the polymerization - ^ a lighter dimensioning of the cocatalyst and, compared to cocatalysts which consist of organic halides, allows especially when one takes into account the very high purity that they must have, a more economical process management.

For illustration, reference is made to FIG. 1, in which a catalyst system according to the invention is compared with known systems.

In FIG. 1, the logarithm of the molecular weight of the isobutylene / isoprene copolymer against the reciprocal value of the polymer oxidation temperature in degrees Kelvin (on the abscissa ^ £ $ && $. \ · _Η Ί? ^K » ^{in the} range

BATH ORIGINAL

from 4 to 6 and the corresponding ⁰ C in the range from -JO "to -96) plotted for copolymerization reactions which are carried out with the systems J ₂ + Al Et ₂ J (curves a and a ¹ ), HGl + (curve b), AlCl, (curve c) and AlEtCl ₂ (curve d) were carried out. The colored points indicate AlEt ^ I concentrations of 55.10 "^ M and the empty dots indicate AlEt ₂ I concentrations of 5 × 10 M (Et = C ₀ H ₁ -).

The compounds with the catalyst system according to the invention Those that can be polymerized are those polygons commonly used in cationic polymerizations for gelan-P gene.

They are therefore those compounds which have at least one unsaturation in their molecule, preferably, but not restrictively, have olefinic unsaturation.

You can use unsaturated straight chain hydrocarbons be at least one olefinic unsaturation, optionally by unsaturated or saturated aliphatic, cyclic or aromatic Eeste can be substituted.

This broad group of compounds includes (1) aliphatic monoolefinically or multiolefinically unsaturated hydrocarbons, which can be unsubstituted or substituted by saturated or unsaturated hydrocarbon radicals, (2) unsaturated cyclic hydrocarbons, which are also unsubstituted or substituted by saturated or unsaturated Hydrocarbons can be substituted, (3) saturated cyclic hydrocarbons, by unsaturated hydrocarbon radicals substituted, (A) aromatic hydrocarbons, substituted by unsaturated hydrocarbons. It is It is important that the selected compound has at least one olefinic unsaturation.

The above-mentioned compounds are in principle made of carbon and hydrogen, but they can also

2 09821/0900

contain other different atoms such as oxygen, sulfur, nitrogen and the like. E.g. the compounds epoxies, cyclic or acyclic ethers, sulfides, imines or the like. Sometimes, such as when using cyclic ethers, the olefinic unsaturation is not necessarily due to a possible bing opening.

Preferred compounds are those which have up to 20 carbon atoms contain.

The inventive method can. on only one Compound to provide a homopolymer, or to two or more compounds to form a copolymer or a polycopol- · mereszu are applied. The working conditions are in Dependency on the monomers used according to those skilled in the art well-known points of view selected.

When the olefins are used, those are used which are used in cationic polymerization. A classic one An example from an industrial point of view are the compounds that form butyl rubber.

The isoolefin used in this way is a compound having 4 to 7 carbon atoms, such as isobutene, 2-methylbutene, 5-methylbutene-1, 2-methylbutene-2 and ^ -methylpentene.

The multiolefins are generally conjugated diolefins with

4 to 14 carbon atoms, such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene Etc.

The greatest number of examples which illustrate the present invention have been started with isobutylene and isoprene in the amounts generally used for the production of butyl rubber, i.e. 95 to 99.5% by weight of isobutylene and 0.5 to

5% by weight isoprene.

The solvents used are those generally used in the manufacture of butyl rubber, i.e. ethyl or methyl

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BADORfGfNAL

215A635

- 6 chloride, methylene chloride etc.

However, it can also. (1) E.

hydrogen solvents which are "liquid at reaction temperatures, such as pentane, isopentane, n-heptane, cyclohexane, ethylcyclohexane, or (2) solvents which are" kept in the liquid phase at the reaction temperature, such as the monomers used or one of the solvents mentioned above, can be used.
The molecular weight of the available polymers can vary within wide ranges depending on the reaction

mern,

participate / the catalyst system and the selected working conditions.

^{The 1} catalyst system according to the invention contains:

a) a reducing aluminum compound "and

b) a compound which reacts with a) to form a positive halogen ion and preferably:

a) a compound such as Al Rp X, in which R is a hydrogen atom or a hydrocarbon radical with up to 8 carbon atoms, and 7. is the same as R or a halogen atom,

such as bromine, chlorine, fluorine and iodine, which with

b) a compound which reacts with a) to form a positive halogen ion and which has the formula YZ, where Y and Z can be identical or different and are iodine, chlorine, bromine or fluorine, is mixed.

The compound a) can also be formed in situ - according to a known method - by reaction of an aluminum halide with an aluminum mechanical connection or an aluminum hydride.

The molecular weights of the polymers, which are according to the following Examples obtained were made by viscometric Measurements of solutions of the polymer in cyclohexane at

certainly.
50 ⁰ C / After the intrinsic molar viscosity numbers by extrapolation of the In | _r / c and -. = "h / c curves at c = O were calculated,

209821/0900 BAti ORIGINAL

de the average molecular weight of the polymers is calculated by the following expression ":

In M _v = 11.98 + 1.452 In [- ^ 3

The following non-limiting examples illustrate the invention. It was therefore preferred to illustrate the invention by the specific case of butyl chewing gum manufacture because of the industrial interest therefor and because the differences from the prior art are more obvious. Based on the above example and from the foregoing description any expert can realize many applications of the present ¹⁵ IRj Lidung without leaving the scope of this invention.

example 1

In experiment 1 (Table A), 9 cc methylene chloride were introduced through a vacuum tube into a Pyrex reactor with a magnetic stirrer; In the Eeaktor two glass vials previously were introduced, 192 mg of AlEt ₂ ^ bzw.8,6 mg J ₂ contained.

The Eeaktor was immersed in a thermostatisierceε bath at -78 ° C and after reaching thermal equilibrium, the two above-mentioned glass ampoules were broken.

The solution thus obtained was then cooled in liquid nitrogen, and 4.10 g of isobutylene and 0.154 g of isoprene were introduced into the reactor through the vacuum tube. When using these amounts of monomers, the isobutylene concentration in the solution was 4.36 mol per liter and that of isoprene 0.14 mol per liter at a concentration ratio of 97 ϊ 3

The Eeaktor was then quickly in a thermostated to -60 ° C Bad transferred. The temperature of the solution quickly reached the bath temperature with stirring.

The copolymerization was continued for 4 1/2 hours, where-

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after the reactor was opened and a few drops of a mono-alkaline methanol solution were added to destroy the catalyst system. N-Heptair was then added to completely dissolve the polymer. The polymer solution was removed from the reactor and the polymer was precipitated in methanol with vigorous stirring.

Experiments 2, 3, 4, 5 (Table A) differ from that the above-mentioned experiment only because of the different temperature "at which they were carried out.

Bt The yields of polymers obtained are also shown in the table A to be taken together with the average molecular weight, which by viscometric measurements as above be. · Was written, received.

The change in the logarithm of the mean molecular weight?, · Ε with the reciprocal of the absolute reaction temperature can be seen from the attached graph.

Example 2

In experiment 6 (Table A), 11.5 ecm of methylene chloride were passed through introduced a vacuum tube into the reactor described in Example 1, in which two glass ampoules with 21 mg AlEtpJ resp. 11 mg of J ^ were introduced.

After the reactor was thermostated to -78 ° C, were the glass ampoules broken.

The solution thus obtained was cooled in liquid nitrogen and 4.8J g of isobutylene and 0.170 g of isoprene were added. Thus the solution had an isobutylene concentration of 4.16 m and an isoprene concentration of 0.16 π at a concentration ratio of 97: 3

The reactor was then transferred to a bath thermostated at -45 ° C., in which the reaction was continued for 4- 1/2 hours.

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BA0ORtÖiNÄt

Regarding the isolation of the polymer, the yield and the loading The procedure for determining the average molecular weight was as in Example 1.

Experiments 7 »8» 9 and 10 (Table A) differ from the one mentioned above only in the different iodine concentrations in the catalyst system. Experiment 10 was carried out without iodine, whereby a very small amount of polymer was obtained after 4 1/2 hours (yield = 5 %)

Example .3

In Run 12 (Table A) were 8.1 cc methylene chloride introduced through the VakuuffjO ^ r in the reactor described in Example 1, wherein two glass ampoules containing 14.8 mg J bzw.7,8 mg J were _0th

'After the reactor was thermostated to -78 ° C, were the two glass ampoules broken.

The solution thus obtained was cooled in liquid nitrogen and 3 »42 g of isobutylene and 0.129 g of isoprene were added.

Thus, the isobutylene / in the solution was 4.36 mol l and the isoprene concentration 0,14MoVl at a concentration M ratio of 97: 3 · The reactor was then transferred to a thermostatic bath to -20 ⁰ C and the reaction was 20 minutes continued.

The tests 13, 14, 15 »16 and 17 (Table A) differ differ from the above due to the different temperature and reaction time.

The change in the mean molecular weight with the reciprocal of the absolute reaction temperature is the one attached to be taken from the graphic representation.

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Example 4

In Experiment 18 (Table A), 18.6 ecm of methylene chloride in the reactor of Example 1 was introduced, in which there were already two glass ampoules with 52 mg AlEtpJ and 11.5 mg Jp.

After the Eeaktor was thermostated to -78 ° C, were the two glass ampoules broken.

The resulting solution was cooled in liquid nitrogen, after which 1.08 g of isobutylene and 0.04 g isoprene were added. Thus, the isobutylene concentration in the solution was 0.97 mol / l, the isoprene concentration 0.03 mol / l at a concentration ratio of 97 ^: 3.

The reactor was then placed in a ⁰ C to -45 "hermo st ac. Transferred, fourth bath, w> rir .the reaction for 4 1/2 hours was performed.

Experiments 19, 20, 21 and 22 (Table A) differ from the above only due to the different concentration of the monomers used.

Example 5

fe In Experiment 23 (Table A) 13 »7 ecm of methylene chloride in introduced the reactor of Example 1, in which there were already two glass ampoules with 25 mg AlEtpJ and 8.4 mg JCl.

After thermostatting to -78 ⁰ C, the two glass ampoules were crushed.

The solution thus obtained was cooled in liquid nitrogen, and 5.76 g of isobutylene and 0.21 g of isoprene were added.

the
Therefore, / isobutylene concentration in the solution was 4.36 mol / L and the isoprene concentration was 0.14 mol / L at a concentration ratio of 97; 3 · The reactor was then in a thermostated to ^'0 -45 C Bad.überführt where the reaction for 4 1/2

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Hours was carried out *

After this time, a polymer was obtained with an average molecular weight of 390,000 (yield = 96%).

Examples

In experiment 1 (Table B), 15.2 ecm of ethyl chloride were introduced into the reactor of Example 1, which contained a glass ampoule with 27.8 mg AlEtpI and a glass ampoule with iodine in such an amount that the reaction solution had a Jp- V ^ nz ent isation of 2.2 x 10 ~ ⁵ m / l.

After the reactor was thermostated at -78 ° C, were, the glass ampoules broken.

The solution thus obtained was cooled in liquid nitrogen and 6.42 g of isobutylene and 0.24 g of isoprene were added to it. The solution thus had an isobutylene concentration of 4.36 Mo3 / l

and an isopron consent. of 0.14 mol / l at a concentration ratio of 97: 3

The reaction was then wälirend conducted for 2 hours at -4 ^ ⁰ C.

There was a Polyir.pres obtained in a yield of 100% with g an average molecular weight of 140 000th

Experiments 2, 3, 4 and ^c j (Table Γ>) differ from the above only in the different temperatures at which they were carried out.

I'm trying. 6, a double filtration of the two monomers compared to that of experiment 1 was used, while the others Paranetei · were kept constant.

Example 7

In Experiment 7 (Table B), 10.8 ecm of methyl chloride were added to the Introduced reactor of Example 1, in which there are already two

209821/0900

Glass ampoules rait 19.4 mg AlEt ₂ J or 9.2 mg J ₂ were.

After the reactor was thermostated to ~ 78 ° C, only the ampoule with AlEtpJ broken. ■

The solution thus obtained was cooled in liquid nitrogen, and 4.44 g of isobutylene and 0.170 g of isoprene were added to it.

The solution thus had an isobutylene concentration of 4.36 mol / l and an isoprene concentration of 0.14 molA at a concentration ratio of 97 ' 3.

'"*""The reactor was then transferred into a thermostated to -60 ⁰ C bath.

No polymer had formed after 11/2 hours. Then became the ampoule filled with Jp was broken and the reactor was opened kept with stirring in the thermostated bath for 2 hours.

In the end, a polymer was obtained with 100% yield, which had an average molecular weight of 420,000.

Examples

In a 300 cc large tubular reactor with mechanical stirrer, which was kept in a thermostatic bath to -50 ⁰ C, the air was displaced pure nitrogen and then 80 cc of methylene chloride were condensed therein. Then 26.4 g of isobutylene and 0.82 g of isoprene were introduced along with 3.6 mmol of AlEtpJ. The copolymerization was started with stirring by adding 0.015 mmol of I ₂ and continued for 15 minutes. After the reaction was stopped by adding a few drops of methyl alcohol to the suspension obtained. \> Was a white elastomer made

. After drying -, - "", which corresponded to a conversion of 68.3%, based on the exnosed isobutylene, and whose [- ^] = 1.39 dl / g (PM = 255,000 ) . The isoprene content was 2.5% (iodo-

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BATH ORIGINAL

metric determination).

The behavior of part of the copolymer obtained in the Vulcanization was determined with a Reometer with an oscillating disk according to Zwick using the following recipe:

Polymer 100 parts

HF carbon black 50 parts

ZnO 5 parts

Circosol oil 5 parts

MBT 0.5 parts

TMTDS 1 part

S 2 parts

Temperature 145 ° C

Samples of the cured polymer were dynamometric tests subject to the following ASTM regulations:

Module D-412 (D hollow punch)

Tensile strength D-412 "Elongation at break D-412"

permanent deformation

after the break after

10 minutes D-412 "

Shore A hardness' - ■ D-676

A comparison of the properties of the product according to the invention having the properties of a commercially available butyl rubber showed no significant difference.

Example 9

The foregoing example was repeated, were ^edocn j 4.0 mmol AlEt ₂ and Ol 0.15 mmol ICl used.

The reaction was continued for 45 minutes, whereupon 16.5 g of a polymer with [η,] = 1.47 dl / g (PM _v = 282,000) and an isoprene content of 2.4% were isolated.

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B e. I s ρ i e 1 10

The previous example was repeated "at -30 ⁰ C and using 0.083 mmol ICl.

After a polymerization time of 30 minutes, 12.75 g of an elastomer were obtained (isobutylene conversion 48.6%) with [ijj = 1.04 dl / g (PM _v = 174,000).

Example 11

Der'Versuch was carried out according to Example 8, but 3.9 mmol of AlEt ₂ Br and 0.664 mmol of JBr were used while the temperature was -35 ° C.

A polymerization time of 15 minutes was made. 24.5 g of an elastomer corresponding to a conversion of the isobutylene used of 92.8 % with l> _t ] = 0.83 dl / g (PM ^. = 132,000).

Example 12

Following the procedure in Example 8, the same amounts of solvent, monomers and AlEtpCl were fed into the reactor. The polymerization reaction was started by adding 0.24 mmol of J ^ at -50 ⁰ C and maintained for 90 minutes.

At the end, after drying, 12 g of the polymer were obtained with a conversion of 45.5% with [ij] = 1.40 (PM _v = 260,000) and with an isoprene content of 2.9% by weight.

Example 13

Following the procedure described in the previous example and using the same amount of reactants, the rization started using 0.11 mmol JBr.

The temperature was kept at -40 ⁰ C. After a reaction time of 20 minutes, 21.0 g of the elastomer (conversion 80%) with an isoprene content of 2.8% and a PM value of 235,000 were obtained.

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Example 14-

The procedure was as in Example 8, but 3.65 mmol of AlEt were used and the reaction was carried out by adding λ ΐ \ Γ \ ττ, τ-ι ^ ι .Tm , τη ^ Λ-π-τ, ι-π + - "κτ -, ^ ν, ripm PnI-σ-τηρ-pi RT ATPTi bp.n -SO ⁰ C \ ύ \\

mliol JCl started. After polymerization at -50 ⁰ C for 90 minutes the elastomer (conversion 26%) were 6.8 g ■

*> * with an isoprene content of 2.7% and a PM value of 31 100 received.

Example 15

As in Example 8 were the same amounts of in the reactor Solvent, monomers and AlEtpCl (4-, 0 mmol) introduced.

The polymerization reaction was "" per'i -50 ° C by adding 0.2 mmol bromine started and continued for 5 minutes.

After drying ν 23 S of the polymer (96% conversion) are obtained with [η] = 1.75
Isoprene content of 3 _S 3% by weight.

treatment) obtained with [η] = 1.75 (PM _V = 350 000) and with a

Example 16

The previous example was repeated, the reaction became but started with 0.06 mmol of chlorine and continued for 5 minutes.

After drying, 20.6 g of the polymer (81% conversion) was obtained with [^] = 1
pren content of 3 »9% by weight.

lung) obtained with [^] = 1.60 (PM = 305 000) and with an iso

209821/0900

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2098 2 1/0900

(Continued) Table A
Experiment Ήτ. [C.3 * [C _n -] * [AlEt ₀ J] ** [J ₀ ] ** Temp. PM (χ 10 ⁵ ) Yield time

20. 4.36 0.14 20 2.2 -45 316 85 270

21 7.28 0.22 20 2.2 -4-5 165 6 "270

22 9, ^ - 1 0.29 20 2.2 -4-5 132 6 270

23 4-, 36 0.14-5 JCl-2.2-4-5 390 96 270

NJ '■■ -.-

cc remarks:

Ü * Mol / 1. '.

^ ** ΙΟ " ⁵ moles / 1

«P · Solvent: CH ₀ Cl ₀ ; C, / O ₁ - »97/3

° PM: mean molecular weight

attempt No solvent CC ₄ ] * CC ₅ ] * Table B. CJ ₅ ] ** Temp. yield PM (x10 ^5th ) Time CAlEt ₂ J] ** ( ⁰ C) (%) (Min.) 1 C ₂ H ₅ Cl 4.36 0.14 2.2 -45 100 140 120 2 C ₂ H ₅ Cl 4.56 0.14 5 2.2 -50 94 10 120 3 C ₂ H ₅ Cl 4.56 0.14 5 2.2 -60 55 320 120 4th C ₂ H ₅ Cl 4.56 0.14 5 2.2 -70 16 25O 120 to 5 C ₂ H ₅ Cl 4.56 0.14 5 2.2 -78 1 ___ 120 C.
cc 6th C ₂ H ₅ Cl 8.73 0.27 5 2.2 -45 100 25O 120 CX!
Ν. · 7th CE, Cl
3 4.56 0.14 5 2.2 -50 100 420 120 °° "^
O Remarks: 5 co
O
O

* Moles / l

*. * 10 " ⁵ Mon 1/1

C ₄ / C ₃ = 97/3

PK = mean molecular weight

ι cn -P - CD

Claims (1)

Claims 1. Catalyst synths for cationic polymerization fully unsaturated compounds, characterized »that a) a reducing aluminum compound of the general formula AlEpX »where R is a hydrogen atom or a hydrocarbon rest with "up to 8 carbon atoms, and X R or an Hplogenatom "mean, and b) a compound, plural marriage under the reaction conditions for Is capable of releasing positive halogen ions, contains. 2. catalyst system according to claim 1, characterized gekennzeichrcb, that the connection b) a connection of the general Formula YZ is where X and Z, which are the same or different, are 1αη can mean "iodine, chlorine", bromine or fluorine. 5 · Catalyst system according to one of the preceding . Claims, characterized in that the connection a) present in a larger molar size than compound b) is. 4. catalyst system according to claim 3, characterized in that that the ratio of the compounds mentioned in claim 1 under a) to the compounds mentioned under b) in the range from 0.1 to 1000. 5 · Process for the catalytic polymerization of unsaturated Compounds, characterized in that (i) the introduces unsaturated compound into a reaction zone, wherein it is in the liquid phase with a catalyst system from a compound of the general formula AlL ^ X. in the R and X have the above meaning, and from a compound which under the reaction conditions to give off positive Halogen ions is capable of bringing into contact, the reaction at such a pressure and such a temperature 209821/0900 BATH ORIGINAL is performed so that a liquid phase ensures the system and (2) isolates the polymeric product. 6. The method according to claim 5 »characterized, that the liquid phase from a Reaktioiismedium,. selected ordered under the aliphatic, aromatic, cycloaliphatic mono- and polyhalogenated hydrocarbons. 7. The method according to claim 6, characterized in that the reaction medium is a halogenated hydrocarbon, such as methyl chloride, ethyl chloride and methylene chloride is. 8. The method according to claim 6, characterized in that the liquid phase by an excess of at least one the unsaturated compounds to be polymerized, which itself is fluid or under an event Pressure and a suitable temperature is liquefied, is formed. 9. Method according to one or more of the preceding Claims, characterized in that the for the delivery of Compound capable of positive halogen ions has the general formula XZ, in which Y and Z are as defined above. 10. The method according to one or more of the preceding claims., Characterized in that the polymerization reaction at a pressure between 0.3 and 3 atm. and is carried out at a temperature between +30 and ^'0 -100 C. 11. Method according to one or more of the preceding Claims, characterized in that at least one monomer which has an olefinic unsaturation; and up to 15 Has carbon atoms is used. 12. The method according to one or more of the preceding claims, characterized in that at least one monomer, which is more than an olefinic 209821/0900-BAD ORIGINAL Saturation and containing up to 20 carbon atoms is used. 1Y. Method according to one or more of the preceding Claims, characterized in that at least one aromatic monomer with mono- or polyolefinic Unsaturations and with a total of up to 15 carbon atoms is used. 14. The method according to one or more of the preceding claims, characterized in that at least one cyclic compound with one or more unsaturations in the ring or with mono- or polyolefinic unsaturations containing substituents used. 15 · The method according to any one of claims 10 to 14, characterized characterized in that the compounds Aa molecule in addition to carbon and hydrogen also other atoms, such as oxygen, sulfur or nitrogen. 16. The method according to one or more of the preceding claims, characterized in that at least two vex "different monomers, such as mono- or polyolefinically unsaturated Hydrocarbons or unsubstituted or substituted cyclic hydrocarbons can be used. 17 «The method according to claim 16, characterized in that that the two monomers are isobutylene and isoprene. 18. Polymers obtained according to the method and using the catalyst system according to one or more of the aforementioned claims. 9821/0900 Blank page