DE2257480A1 - PROCESS FOR THE PRODUCTION OF POLYMERS AND COPOLYMERS OF ISOBUTYLENE - Google Patents

Description

Dr. F. Zumstelr Sr. ■ Or. E, Assmann Dr. R. Koenlgsberger - Dipl.-Phys. R. Holzbauer - Dr. F. Zumsteln Jun.

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Process for the preparation of polymers and copolymers of the

Isobutylene.

The invention relates to a method for producing polymers and copolymers of isobutylene using a special catalyst system that allows the use of higher reaction temperatures, than they were previously used industrially. It also enables higher yields to be achieved on polymers with a higher molecular weight and in general better characteristics, of course, from the chosen working conditions and others, in this technical field the usual factors. In particular, the invention relates to the manufacture of butyl rubber.

It is known that butyl rubber is industrially produced by a copolymer isation method is produced using Cationic initiators work.

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2257A80

In particular, the copolymerization is carried out using AlCl- dissolved in ethyl chloride or methyl chloride at -100 ⁰ O. The use of a solid catalyst insoluble in common hydrocarbon solvents and only sparingly soluble in solvents containing chlorine has many difficulties in realizing an effective control thereof Reaction brought with it.

The production of the catalyst solution is already somewhat complex and is generally obtained by passing a stream of ethyl chloride or methyl chloride onto a bed of solid aluminum trichloride realized.

The subsequent determination of the concentration of the catalyst, which is carried out by titration of the AlCl is very complex and often leads to completely unexpected results. From the The foregoing appears to have been in the past by researchers and industries interested in making this Kautachukart are, many efforts have been made to create new catalyst systems, which at the same time the problems of • Dosing the catalyst and raising the polymerization temperature could solve the problem without obviously affecting the properties of the rubber and in particular without reducing the value of the molecular weight. Perfected in recent times some scientists developed a new soluble catalyst that can produce buty! rubber at a high level Molecular weight at temperatures considerably higher than those usually used in industrial processes, enables.

This system is derived from the combination of a "modified" Priedel-Crafts halide, for example AlAt ₂ Cl, with a suitable cocatalyst. These halides generally do not allow the polymerization of isobutylene or mixtures of isobutylene and diene monomers or other monomers which normally polymerize by a cationic type mechanism to be initiated on their own. The polymerization or copoly-

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merization only begins when the cocatalyst is introduced will. This cocatalyst can be composed of a substance that can generate protons, such as HOl and other Brönsted acids or from a substance called carbonium ions can deliver, such as t-butyl chloride.

The German Offenlegungsschrift 2 154 634 concerns. a Process for the production of butyl rubber using a catalyst system from a reducing Aluminum compound and from a cocatalyst that can provide cations to interact with the catalyst. Of the Cocatalyst can be a halogen introduced as such or other interhalogen compounds.

The present invention is an improved method, which has now been found that all the advantages of the catalyst systems listed above have essentially with the considerable ease of controlling the polymerization reaction are connected. This is due to the solubility of these catalysts in common organic solvents, so that if this is necessary, the possibility exists, with minimal amounts of solvent, even in the complete absence of solvents work, in which case the unreacted monomer serves as a diluent.

Regarding the method using dialkyl aluminum halides and strong acids, it differs greatly in the use of real cocatalysts, which are themselves inactive and Form a polymerization catalyst only through interaction with the other components of the system. Furthermore show the catalyst systems according to the invention have a milder activity, whereby an easier control of the polymerization reaction is possible and in this way a polymer is created which has physically more favorable properties for industrial implementation because of the finer distribution of the elastomer lumps, generated during the polymerization.

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Finally, "it possesses in terms of the system, the halogen or Interhalogen solutions used, the great advantage with respect to the compounds used as catalysts, are easier to handle to be able to.

Even if the present description focuses essentially on the manufacture of butyl rubber, because of the industrial interest on this substance, it is easy for the person skilled in the art to find the ideal for the catalyst system described here To find conditions for the copolymerization of different monomers.

In particular, the monoolefin which can be used can have a number of carbon atoms from 4 to 7, whereas the polyunsaturated olefin is generally comprised of conjugated Diolefins with a carbon number from 4 to 14 (C. - C ^) such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene; Examples for the former can be: isobutene, 2-methylbu- · ■ -ten- (i), 3-methylbutene-d), 2-methylbutene- (2), 4-methylpentene- (i) .. In the manufacture of butyl rubber, which is of great industrial interest, isobutylene and isoprene are used in quantities from 90 to 99.5% by weight of isobutylene and from 10 to 0.5% by weight Isoprene copolymerized.

The reaction media used are customarily used in this technology used, used, such as ethyl chloride, methyl chloride or methylene chloride. Hydrocarbon compositions can also be used which are liquid at the reaction temperature, for example pentane, isopentane, n-heptane, cyclohexane, or even Solvents that are in the liquid phase at the reaction temperature are retained, such as, for example, the monomer or the monomers used.

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The molecular weights of the product obtained vary within a wide range depending on the conditions used.

The catalyst system of the invention comprises:

a) an organometallic compound of aluminum with the formula AlFU or AlR ₂ X, in which X is a halogen atom and R is a hydrocarbon radical having 1 to 10 carbon atoms or hydrogen;

b) a compound of the formula X ¹ MeY _m> wherein X 'is a halogen atom; Y is oxygen, sulfur or a functional group selected, for example, from the alkoxy groups (-OR), esters (-O-COR), amides (-NR ₂ ), substituted or unsubstituted alkyl groups (-R), cycloalkyl groups (-C ), Aromatics (Ar), arenes (delocalized bonds between pseudoaromatic rings or aromatics and transition metals), phosphines (-PR ₂ ), acetoacetyl groups (-COCH ₂ COCH ₂ R), oximes (= C = NO-), where R is the above has listed meanings .; Me is an element selected from: Ti, Sn, Zn, Si, B, Al, Hg, Pb, W, Sb, Ge, V, Zr, As, Bi, Mo; η and m are integers the sum of which is equal to the valence of Me, except for the case where Y is oxygen or sulfur, which becomes 2m + η.

Specific examples of these cocatalysts are: TiCl ₅ (OR), RSnCl,, R ₃ SnCl ₂ , R ₅ SnCl, (ArylUSnCl, RZnCl, HSiCl _?, RSiCl,, R ₉ SiCl ₂ , Cl ₂ Ti (QCOCH ₅ ) ₂ , R ₅ SiCl, BF ₉ OR, AlOCl ', RHgCl, R ₂ PbCl ₂ , WCl ₅ (OR), WCl ₄ (OR) ₂ , C ₅ H ₅ TiCl ₅ , SnCl ₅ (NR ₂ ), (CgH ₅ USbCl ₂ , CH ₅ GeCl ₅ , Ti (acetoacetyl) ₂ Cl _?, VC1 ₂ (MR ₂ ) ₂ , ZrCl ₂ (OCOCH ₅ ) ₂ , Cl ₂ AsOR, CH ₅ AsI ₂ , ArBiCl ₂ , Ar ₅ SbCD ₂ , SiOCl ₂ , ZrOCl ₂ , TiOCl ₂ , SnSCl ₂ , RSnSCl, SnOCl ₂ , RSnOCl, CH ₅ COOSnOCl, RPbOCl, VOCl ₂ , MoOCl, MoOBr, MoOCl, (Ar = aryl).

The catalyst may be prepared in advance or, preferably, the cocatalyst, is added portionwise in _o a second phase in the reaction medium. The molar ratio

but between the total amount of compound b) and compound

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a) is always below 1, preferably between 0.5 and 10 ~.

The molecular weights of hergestell th in the following examples, polymers were determined by viscometric measurements of polymer solutions in cyclohexane at 30 ⁰ C. After determining the intrinsic viscosity by extrapolating the curves tin \\ _T / _Q and in ^ ₈₁₅ /, ' ^oe * ^{c =} ° * ^{, the} average molecular weight of the individual polymers was calculated according to the following equation

In M _v = 11.98 + 1.452 £ n [^]

I j,

calculated.

The following examples serve to illustrate the invention without restricting it.

example 1

In a tubular reactor made entirely of glass, with a capacity of 300 cm, equipped with a mechanical stirrer and a thermometer sleeve, which was previously heated with a flame under a stream of dry argon and which during the implementation of the example under a slight argon overpressure (20 - 30 torr, based on atmospheric pressure), 80 cmr of CH, C1 were condensed and then 28.4 g of isobutene, 0.84 g of isoprene and 0.254 cnr (2 mmol) of AlAt ₂ Cl were introduced, the temperature with a thermostated bath was brought to -4O ⁰ C.

The reaction mixture, kept under vigorous shaking was then gradually with 0.15 mmoles of Ti (0-nC ^ Hq) CI * dissolved in CH-ZCL, for 12 minutes, added, whereupon the temperature of the Reaktionsmischunc increased by 4 ⁰ C. It was shaken for a further 5 minutes after the addition had ended and the reaction was then stopped by adding methanol to the suspension of the polymer formed.

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19 * 65 S (69 * 3 % yield) of dry polymer were obtained! with a "value for [Q], determined in cyelohexane, of 2.20 dl / g, which corresponds to an average viscometric molecular weight of 480,000, and with a content of unsaturated bonds, determined iodometrically, corresponding to 3.15 % isoprene Weight The average molecular weight in M numbers, determined with a Mechrolab apparatus Mod. 502, was 226,000. The polymer was also measured with a GPC apparatus (Mod. 200 Waters Ass.) Using trichlorobenzene as a solvent at a temperature studied of 130 ⁰ C, to obtain the distribution curve of the molecular weights.. This gave a monomodal distribution curve of the molecular weights, resulting in a value for

rj = 2.4. The same determination made on different

various samples of commercially available butyl rubber

..M
Values for __w_ _between and including 2.1 and 2.6.

The polymer obtained was in the form of cut flakes using a mixture of the following composition, which was produced in an open mixer with cylinders, vulcanized:

Polymer 100 Parts EPC carbon black - 50 ti Antioxidant 2246 1 11 ZnO 5 11 Stearic acid 3 It sulfur 2 11 MB-TSD- (Mercat) tobenzthiazole- disulfide) 0 .5 " TMTD (tetramethvl-thiuram- disulfide ^ 1 11

The mixture was vulcanized at 153 ° C for 40 and 60 minutes. The properties of the vulcanized products obtained are shown in Table 1? in Table 2 are for comparison purposes the properties of a commercially available butyl rubber, determined under the same conditions.

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Table 1

Vulcanization time
Module at 100 % (kg / cm ² )
Module at 200 % "
Module at 300 % "
Breaking load "
Elongation at break {%)
permanent deformation

40 60 cm ² ) 16 19th 29 35 Jx ₇ 6o 214 215 730 670 W. 37 35 Table 2

Vulcanization time ^w (minutes) 4θ 6θ

Module at 100 % (kg / cm ² ) 15 16

Module at POO % "27 33

Module at 300 % "47 58

Breaking load "209 210

Elongation at break (%) 715 650

permanent deformation {%) 29 29

■ ' Butyl rubber Enyay B 218 with a viscometric molecular weight of about 450,000 and a content of unsaturated bonds, corresponding to 2.15 % isoprene weight.

The results listed above that which has in this example at -36 to -4o ° C obtained polymers after its vulcanization properties similar to those of a commercial Butylknntschuks, as is known, is at a temperature below -100 ⁰ C 'f ^ Rtnllt, equal to are.

BoI r, pi pi P

The previous example was carried out with the same amount of P tien, except that Koin AlKt ₉ Cl was used, but Ti (OnCj ₁ H ₀ ) Cl ^ in an amount five times that of the previous D ^ i game (ir ..sn; it «nt-. 0.75 mmoles). No patient was formed during this process.

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This example shows that Ti (O-H-C ^ Hq) CI-, not by itself the Polymerization of the reaction mixture used can start, even in concentrations that are considerably higher than the in Example · 1 used lying.

Example 3

Example 1 was repeated, except that a solution of 0.3 mmol Ti (0-nC ^ HQ) ₂ Cl ₂ in CH ^ Cl was used as cocatalyst. The addition took place at a temperature of -40 ⁰ C for three minutes, and it was further shaken for 20 minutes. No polymers were formed; not even after another addition of

2 moles of AlAtpCl. This example shows that that obtained in Example 1 Catalyst activity does not occur. Exchanges between the Al-alkyl and the Ti-alcoholate are recycled can, but strictly on the type of Al-alkyl used and Alcoholates depends.

Example 4

According to the methods described in Example 1 were in the reactor introduced the same amounts of solvent, monomers and AlÄtpCl.

The reaction was carried out at a temperature of -4o ° C by gradual Introducing a solution of 0.4 mmol Si (CH ^ JpI, in CH, C1 started for 4 minutes, the temperature rising by 2 ° C. 5.5 β (19.5 # yield) of dry polymer were obtained! with a value for [ip] of 2.45 dl / g (MW = 570,000) and with a Content of unsaturated bonds, corresponding to an isoprene weight of $ 2.10. ·

The polymer was vulcanized as described in Example 1, and the properties of the vulcanized products are in Table

3 listed.

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Table 3 40 60 ten) 15th 16 24 30th 39 52 207 220 715 680 31 30th

Vulcanication time (minutes)
Module at 100 % (kg / cm ² )
Module at? 00 % "
Module at 300 fo "
Breaking load "
Elongation at break {%)
permanent deformation (#)

The properties of the polymer obtained are therefore very similar to those of typical examples of commercially available butyl rubber.

Example 5

The previous example was repeated, except that no AlAtpCl was used, but Si (CH ^) Cl-, in an amount equal to was five times higher than that used in Example 4 (total 2 mmoles). No polymer formed.

Example 4 was also carried out using the same amounts of reagents and AlntgCl and using 0.5 mmol Si (CH,) -, Cl repeated as cocatalyst, so formed no polymer.

Example 6

According to the methods described in Example 1 were in the reactor introduced the same amounts of solvent, monomers and AlJitgCl.

The reaction was started at a temperature of -4o ° C. by gradually adding a solution of 0.18 mmoles of Sn (C ₂ H ^) -, Cl in CH- * C1 to the shaken reaction mixture, during 2 minutes, the temperature increased by H ⁰ C. 19.75 g (69.5 % yield) of dry polymer were obtained with an IQ] value of 1.79 dl / g (PM _V - 360,000) and an unsaturated bond content corresponding to 3 »2 % isoprene weight.

The polymer was vulcanized as in Example 1, and the properties

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Table 4 40 60 en) ■ 15 17th 25th 29 43 51 209 210 7βθ 68ο 38 35

shafts of the vulcanized product are listed in Table 4,

Vulcanization time (minutes)
Module at lOO fi (kg / cm ² )
Module at 200 % "
Module at 300 % "
Breaking load "
Elongation at break {%)
permanent deformation {%)

As can be seen from Table 4, the properties of the polymer are those of a typical commercial sample of butyl rubber very similar (see Table 2).

The sample was also examined with a CPC apparatus (Mod. 200 Waters Ass.) As described in Example 1. One received a monomodal curve for the distribution of molecular weights,

K
"from which a value of π - = 2.67 was obtained.

η
Example 7

The previous example was repeated, but no AlÄ'tpCl was used, but Sn (CpH, -)., C1 as such, in Amounts five times greater than those listed in Example 6 (0.9 mmol). No polymer formed.

Also when Example 6 is repeated using the same Amounts of reagents and ^ lXtgCl and using 0.36 mKol No Folymeres was formed as a cocatalyst.

Example 8

Example 6 was repeated, except that a solution of 0.05 mmol of Sn (CpHc) Cl-Z in CH-zCl was used as cocatalyst and was slowly added to the reaction mixture over a period of 6 minutes at a temperature of -4o ° C., the Temperstur around. 18 C pn rose. This gave? 5j3 g (89 fo yield) of dry polymer

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22 57 A 8.0

with a value for [ Q ] of 1.40 dl / g (PM _y = 250,000) and a content of unsaturated bonds, corresponding to 5 * 05 % isoprene weight.

Repeating this example using by itself, without the AlAtpCl, in amounts five times greater than that above (0.25 moles in total), no polymer was formed.

Example 9

Example 6 was repeated, except that a solution of 0.05 mmol of Sn (CH -,) pClp in CH, C1 was used as cocatalyst and was slowly added to the reaction mixture over 5 minutes, the temperature rising by 7 ° C. 18.1 g (64 % yield) of dry polymer were obtained! with a value for [n] of 1.88 dl / g (PM _V = 580,000) and a content of unsaturated bonds, corresponding to 2.85 % isoprene weight.

When repeating this example using Sn (CH -,) oCOo alone without AlÄtpCl, in amounts five times that listed above (total 0.25 mmol), none were formed Polymers.

Example 10

The procedure was as in Example 1, except that a solution of 0.5 mmol of SiHCl-5 in CH-, C1 was used as cocatalyst, which solution was slowly added to the reaction mixture over a period of 8 minutes, the temperature rising by ° C. 14.7 g (51 »8% yield) of dry polymer having a value ^ for [* \] of 1.63 dl / g (PM _V = 3i5 000) and a content of unsaturated bonds corresponding to 2.2 f > Isoprene weight.

When the example was repeated using SiHCl, alone, without AlKt ₀ Cl, in amounts five times the above (total 2.5 mmol), no polymers were formed.

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- 15 example - 11. .

The above example was repeated, except that 1 mmol of AlAt ₂ Br was used as the catalyst and a solution of 0.4 mol of SiHCl in CEUCl was used as the cocatalyst. The addition took place at -40 ° C for 9 minutes, the temperature rising by 5 ° C. 25 * 4 g (89 * 5 % yield) of dry polymer were obtained! with a value for [r ^] of 1.55 dl / g (PM _V = 990,000) and a content of unsaturated bonds of 3 * 15 $ isoprene weight.

Example 12

The procedure was as in the previous example, but using the catalyst. 2 mmol AlÄ'tpI and used as co-catalyst, a solution of 0.6 mmol of Sn (CH-Z) ₀ CIo * in CH ^ Cl was that was added to the reaction mixture over 3 minutes, keeping the temperature at 4 ° C increase. 16.37 g (5 * 6 % yield) of dry polymer were obtained! dl with a value for ^r [fj_] of 1.41 / g (PM _V = 250 000) and a content of unsaturated bonds in accordance 2.22 $ isoprene weight. ·

* (or Sn (CH ₅ I ₃ Cl)
Example 13

The procedure was as in the previous example, except that 2 mmol of AlA'tpF was added as a catalyst and a solution of 0.32 mmol of Sn (CH ^) ₂ Cl ₃ in CH ^ Cl 3 was added to the reaction mixture over the course of 3 minutes, the Temperature increased by 1.5 ° C. 4.88 g of dry polymer were obtained with a value for [f)] of 1.55 dl / g (PM _V = 250,000) and a content of unsaturated bonds corresponding to 2.6 % isoprene weight.

Example 14

The previous example was repeated, except that 2 mmol of AlKtpCl was used as the catalyst and a solution of 0.22 mmol of Sn (C ^ Hp -) ^ Cl in CH-, C1 was used as the cocatalyst, which was added to the reaction mixture over 14 minutes. the temperature rising ^{by 5 ° C.} 20.75 g (79 % yield) of dry polymer with a T value for [ty] of 1.3 dl / g (PM _V β 240,000) and a content of unsaturated bonds were obtained

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2257A80 - i4 -

corresponding to 2.4 % isoprene weight.

-Cl alone, without AlÄtpCl, started the polymerization not even when using amounts five times that layers used in this example.

Example I5

It was worked as in the previous example, but were being used as Cokntalysator 0.4 mmol Ti (OCOCHOpCl ₂ and was slowly added at a temperature of ⁰ -4o C for 3 minutes, keeping the temperature at 4 ⁰ C increase. Yt »n received 1?,? 5 Z (53 % 5%) of dry polymer with a value for [η] of 1.66 dl / g (PM _y = 320,000) and a content of unsaturated bonds corresponding to 3 * 15 % isoprene weight. Ti (OCOCH-) ₂ C1 ₂ used for the polymerization alone, without AlAtpCl, did not result in the formation of a polymer under the same experimental conditions.

Example 16

Under the same working conditions as in the previous example, 2 mmol of AlÄ'tgCl and as cocatalyst 0.2 mmol of Sn (OCOCH-) ₂ Clp were used as the catalyst and slowly added at a temperature of -4O ⁰ C for 7 minutes, the temperature around 6 ⁰ C rise. This gave 16.5 g (58% yield) pn dry polymer having a value of [n] of 1.96 dl / g (PM _V = 410 000) and a content of unsaturated bonds in accordance 2.9 ^ isoprene weight.

^{Sn (OCOC 1} H ^) pCl _Oi used for the polymerization ε Hein, ie without Al ^ tpCl, gave no formation of the polymer under the same conditions.

Example 17

The procedure was as in the example described above, except that the solvent CH-Cl was replaced by n-pentane. Furthermore, 2 mmol of AlKtpCl were used as a catalyst and 0.5 mmol of Sn (C ₂ Hc) Cl-, dissolved in n-pentane, as a cocatalyst.

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turns - The cocatalyst was added over 2 minutes, during which the temperature rose by 11 ° C. and a viscous polymer solution formed. In the end, 14.15 g (49.7 % yield) of dry polymer were obtained! with an average viscopimetric molecular weight of 85,000) and a content of n unsaturated bonds corresponding to 2.35 % isoprene weight.

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Claims (10)

Claims \ L A process for the production of polymers and copolymers of isobutylene, characterized in that the polymerisation reaction is carried out in the presence of a catalyst system, which is composed of: a) an organometallic compound of aluminum with the formula AlFU and AlRpX, in which X is a halogen atom and F a hydrocarbon radical with one number of carbon atoms from 1 to 10, or hydrogen; b) a compound of the formula X ¹ MeY, in which X ^{1 is} a halogen atom, Y is oxygen or sulfur or a functional group selected from alkoxy, ester, amide, substituted or unsubstituted alkyl, cycloalkyl groups, aromatics, Arenes, phosphines, acetylaceto groups and oxides; Ke represents an element selected from Ti, Sn, Zn, B, Al, Hg, Pb, V /, Sb, Ge, V, Zr, As, Bi and? ·! Ο; η and m are specific numbers the sum of which is equal to the valence of Ke, but when Y is oxygen or sulfur, the valence is expressed by 2m + η. 2.) The method according to claim 1, characterized in that the molar ratio between the compound a) and the total amount of b) is between 2 and 10,000. 3.) Method gen * ?: 2 one of the preceding claims, characterized characterized in that the polymerization reaction is carried out in the presence of a reaction medium chosen is made of aliphatic, aromatic, cycloaliphatic ^ mono- and polyhalogenated hydrocarbons. 4.) Process according to one of the preceding claims, characterized in that methyl chloride is used as the reaction medium will. 309822/1087 5.) A process according to any one of the preceding claims, characterized in that the Polymerisationsreakt-ioh is carried out at a temperature between +30 ⁰ C and -lOO. 6.) Method according to one of the preceding claims, characterized characterized in that isobutylene is copolymerized with isoprene. 7.) The method according to claim 6, characterized in that the copolymerization reaction by feeding a mixture of
90 to 99.5 wt% isobutylene and from 10 to 0.5 wt% isoprene
is carried out into the reaction zone. 8.) Polymers and copolymer products, obtainable by the process one of the preceding claims and the catalyst systems used there. 9.) Isobutylene-isoprene copolymers with a monomer content of
90 to 99.5 wt .- ^ isobutylene and from 10 to 0.5 wt .- ^ isoprene, obtainable by the process of any one of claims 1 to 8. 10.) Objects and products obtainable from the polymers and copolymers produced according to one of the preceding claims became. · 3098 22/1087 original fNSPECTJSD