DEST004634MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: March 26, 1952. Advertised on March 8, 1956

GERMAN PATENT OFFICE

The PIrfindung relates to a process for the production of copolymers from isobutylene and Diolefins of 5 to 8 carbon atoms at low temperature to produce a relatively strong unsaturated rubber-like copolymer, especially the copolymerization of isobutylene with Isoprene, at low temperature for the production of an elastic copolymer with an iodine number between 55 and 175, which can be vulcanized with sulfur and other known vulcanizing agents.

A number of very valuable copolymers with an iodine number of about 1 to 50 are already available from a mixture of a larger amount of isobutylene with a smaller amount of a preferably conjugated one Diolefins with 5 to 8 carbon atoms, especially isoprene, are produced. The procedure is general in that one is a mixture of a larger part of isobutylene with a smaller part of isoprene on one Temperature between ο and - 164, preferably around - 60 to - iio °, cools and this cold 'mixture by adding a dissolved Friedel-Crafts catalyst polymerized with or without an inert diluent. This reaction is beneficial with Mixtures of a larger proportion of isobutylene and a smaller proportion of isoprene have been carried out and resulted in an excellent polymer which, after vulcanization, has high strength and had excellent physical properties.

509 696 / 50S

St 4634 IVb / 39c

The normal isobutylene-tsoprene copolymer produced in this way has an iodine number of about ι to io. Such a value is sufficient to produce, by subsequent vulcanization, a product with a tensile strength of 126 to 252 kg / cm ² at break. Although this polymer has a high degree of airtightness and has proven to be particularly suitable for automobile hoses, the rate of vulcanization is relatively low.

Vulcanization is too slow, even when using very effective accelerators. In addition, the modulus (these are the values of the tensile stress in kg / cm ² for the respective elongation) is often undesirably low.

It has been found that the polymer has a certain minimum value of the molecular weight and must have the iodine number in order to be vulcanizable to a rubbery solid. These two Factors are related to one another in such a way that they indicate that each molecule has more than one must have a certain number of units of unsaturation left by one not in Reaction resulting from the olefin bond in the bonded isoprene radical. The exact relationship is up to now between the measured degree of unsaturation and that actually present in the polymer Oil bindings have not yet been determined. It has been found that in each case a minimum molecular weight (according to Staudinger) of about 20,000 and an iodine number of 55 to 175, measured according to the usual analytical procedures "are required to achieve a fully satisfactory high rate of vulcanization.

However, to a certain extent these two conditions are mutually exclusive. It was found that the diolefins used in the monomeric starting material, ζ. Β. Isoprene, a specific one Exercise poisonous effect on the catalyst, which is the stronger, the more diolefin is present. the The main effect of this poisoning is that only a lower molecular weight of the polymer can be achieved. In addition, the degree of polymerizability of isobutylene varies with the Olefin within the various diolefins. One example is the ability of butadiene to copolymerize relatively low. There are 30 parts of butadiene per 100 parts of isobutylene necessary so 2 to 3 parts of butadiene are bound in the copolymer. Isoprene is a much stronger catalyst poison.

Its copolymerizability is somewhat greater. About 3 parts of isoprene per 100 parts of isobutylene are sufficient here so that about 2 to 2 ¹ ₂ parts go into the polymeric molecule. However, this highly toxic effect of isoprene on the Friedel-Crafts catalyst makes it impossible to use this compound in sufficient quantities in the starting material in order to achieve the desired high level of unsaturation. Other C ₃ and higher diolefins poison the catalyst just like isoprene, and in some cases are even more effective than this. It was further found that the Staudinger molecular weight depends on the isobutylene yield up to which the reaction is carried out, since the average molecular weight of the polymer drops sharply with increasing yield. The Staudinger molecular weight and the related Mooney viscosity drop sharply when the degree of conversion, based on isobutylene, increases. In order to be able to roll, calender and press the product satisfactorily, the Mooney viscosity is expediently about 25 to 60 or even more; a product of less than 25 Mooney is too soft to cure satisfactorily. Products with more than 60 Mooney are too tough to be processed on their own, but can be used with the addition of plasticizers. However, the lower the bound diolefin content, the lower the iodine number and the poorer the vulcanization properties.

It has now been found that copolymers of isobutylene and isoprene can be produced whose iodine number is above 50, namely in a range from 55 to 175, and whose molecular weights are at least 20,000 and are thus sufficiently high to produce the polymers with good To be able to vulcanize success, either alone or in a mixture with other polymers, eg. B. the known isobutylene-isoprene copolymers of a high degree of saturation. This result is achieved in that a very highly purified diolefin, in particular isoprene, is used in the starting material, which z. B. has a purity of 99 mol percent and more, or by using a special polymerization catalyst, in particular a complex of zirconium tetrachloride and an ether, or finally by using a combination of both features mentioned. In particular, it has been found that the dissolved complexes of zirconium tetrachloride with ethers of a molecular weight of 90 and above, such as β, / 3'-dichloroethyl ether and diphenyl ether, are particularly suitable for the preparation of these more unsaturated copolymers. It is possible to prepare polymers with substantially higher iodine numbers by mixing these highly unsaturated polymers prepared according to the invention with polymers with low iodine numbers, and thereby obtain products with an average degree of unsaturation which, however, is substantially higher than that of the usual isoolefin-diolefin copolymers. It has been shown to be possible to use copolymers from olefinic! Produce starting material which contains 25 to 150 percent by weight isoprene, based on the isobutylene content in the starting material. In comparison, the usual amounts of isoprene, which are used to produce the usual, known isobutylene-diolefin copolymers, are in the range from ι to about 5 and up to 10 percent by weight, based on isobutylene, the most common value being 2.5 to 3, 5 ° / ₀ .

It has been found that the molecular weight, estimated from the Mooney viscosity values, with the corresponding diolefin content in the starting material no further decrease, which is to be expected would have been. Rather, the molecular

696/508

St 4634 IVb I'39 c

weight of the copolymer a minimum and then also decreases with increasing content of diolefin and results in polymers of a satisfactory molecular weight, although larger Di-5 There are olefin quantities in the starting material and the end product is correspondingly more unsaturated. It has been found that this minimum also accounts for a number of processing properties of these Polymers exist, which according to the processing speed in the extrusion press or hose injection molding machine and the swelling on injection can be assessed. For example, the spray behavior the isobutylene-Diolefm copolymers, z. B. also those with isoprene as a diolefin component, a little worse if the iodine number is increased from about 1 to about 50, a value which is considered to be the highest permissible Value for the usual isobutylene-diolefin copolymers produced by means of the known processes was found. In the meantime, polymers with even higher iodine numbers show increasingly better spray behavior.

In view of the striking differences in the effect of a higher iodine number when using an isoprene of a purity of over 99 mol percent, there is a strong probability that isoprene not only acts as a catalyst poison and thereby adversely affects the molecular weight of the polymer, but also that in the Ordinary isoprene contains a different and possibly much stronger catalyst poison. This would explain the fact that, when using isoprene of lower purity, polymers of lower molecular weight are obtained, thereby rendering the products essentially worthless, while, on the other hand, when using isoprene of very high purity, surprisingly, polymers are obtained which not only satisfactory with regard to their molecular weights, but are more unsaturated in ^v very desirable manner.

For example, a typical isoprene of ordinary quality (97.3% / _n isoprene) has the following composition:

Weight. Composition percent

Isoprene 97.3

Pentene-i (some 2-methyl-butene-i) 1.8

Cyclopentadiene 0.2

Piperylene 0.3

α-acetylenes 0.1

Higher boiling (mostly isoprene dimer). .. 0.3

Total ... 100.0

It has also been found that a very good copolymer with both a higher molecular weight as well as a higher iodine number can be produced by a process in which as a polymerization catalyst a complex of zirconium tetrachloride and an ether is used in solution. It is further possible this process using the complex catalyst with the · application of an isoprene to combine very high purity in order to achieve optimal results.

When using the complex catalyst, the polymerization of the olefin emis this, which z. B. contains a major part isobutylene and a minor part isoprene by adding one in solution Brought zirconium-containing catalyst achieved. In the preferred embodiment, the one for the A catalyst used to produce a maximum degree of unsaturation in the finished polymer Complex of zirconium halide and an ether. The zirconium chloride-ether complex is useful in Used in the form of a solution and can be dissolved in an organic solvent for this purpose, which does not react with the catalyst or enters into a further complex bond and at the polymerization temperature is liquid.

For the purposes of the present invention, both the simple lower dialkyl ethers, such as methyl or ethyl ethers, and the higher ethers, such as propyl, butyl and amyl ethers, can be used. Alkyl aryl ethers can also be used. Substituted ethers, such as chlorine-substituted ethyl ether, can also be used satisfactorily. As 8g examples of ethers, which can be used for the production of the zirconium chloride complexes, are mentioned: ethyl ether, di-n-propyl ether, diisopropyl ether, the dibutyl ether, anisole and its derivatives, diphenyl ether, ß, ß'-dichloroethyl ether, α, α'- Dichloro ethyl ether, 1,2-diphenoxyethane, o-chlorophenyl ethyl ether, / 5-chloroethylphenyl ether, diethylene oxide, trioxymethylene and dichloromethyl ether.

The complex catalysts of zirconium chloride and ether are preferably not in solution in one Low freezing point complexing solvent applied. The solvent must at least Dissolve 0.1 percent by weight of the catalyst complex. In addition, the solvent should not have any enter into another complex with the zirconium tetrachloride-ether complexes. As a solvent you can Use essentially any mono- or polyhalogenated alkane whose freezing point is below about - io °, as well as carbon disulfide. Methyl chloride, methyl bromide and di-log are particularly useful chloromethane and ethyl chloride. You can also use hydrocarbon solvents, such as propane and butane and in some cases also pentanes.

A preferred process for the preparation of the zirconite tetrachloride ether complex is that one dissolves the required amount of the complex-forming ether in the alkyl halide and this solution through Zirconium tetrachloride conducts so that the complex is formed in the alkyl halide itself. In this way 11g the concentration of the catalyst in the finished catalyst solution depends on the amount of ether, which was initially dissolved in the alkyl halide.

So far, the known solutions were made of aluminum chloride catalyst in alkyl haloids, e.g. B. methyl and ethyl chloride, prepared by replacing the desired alkyl halide with an aluminum chloride containing cartridge headed. Here, however, is the setting of the concentration of aluminum chloride somewhat difficult in the alkyl halide solvent because the solubility increases with temperature

509 696/508

St 4634 IVb / 39 c

, and changes the flow rate of the alkyl halide, making it necessary to dilute the solution initially obtained in order to obtain the desired concentration. To be most effective, zirconium tetrachloride must be used in solution. Zirconium tetrachloride itself is insoluble in alkyl haloids. Its ether complex, however, dissolves in these. The alkyl halides can serve both as a solvent for the catalyst and as a diluent for the reaction mixture. This procedure is possible because of the formation of molecular complexes of zirconium tetrachloride with numerous ether compounds, such as. B. ß, ß'-dichloroethyl ether, diphenyl ether, isopropyl ether, anisole and various other ethers soluble in alkyl haloids. The preferred method for preparing the catalyst solution offers the further advantage that the amount of zirconium tetrachloride, the catalytically active principle in the finished solution, can be controlled by the amount of ether which is dissolved in the alkyl haloid before it passes through ZrCl ₄ .

The catalyst solution prepared in the manner described above or in any other way is added to the cold mixture of isobutylene and diolefin in atomized Form introduced. The spray is directed onto the surface of the vigorously stirred olefin mixture. You can also use the catalyst solution in each other. Feed manner with which one can rapidly distribute the catalyst solution in the cold olefin mixture achieved. The concentration of the catalyst in the solution can be 0.05 to 15 percent by weight. "The rate of addition of the catalyst solution generally varies between 0.05 and 5 percent by weight per minute, based on the contents of the reaction vessel. By using more Catalyst in a longer period of time gives a higher conversion. In general, about 0.01 to ι weight percent catalyst used. The catalyst effectiveness is about 100 to 10,000 g of polymer produced per g of catalyst. the Polymerization proceeds rapidly and leads to a solid rubber-like copolymer a molecular weight according to Staudinger between 20,000 and 100,000. The lower the polymerization temperature, the higher is the molecular weight if all other conditions remain the same.

In Table I the values for the Mooney viscosity, the Staudinger molecular weight, the degree of unsaturation in mol percent and the iodine number are given for a number of polymers which were obtained according to the invention and according to the known procedure, in which aluminum chloride in methylene chloride as a polymerization catalyst and an isoprene from about o, 6 ° / ₀ purity was used. In general, within each test series with the same isoprene content of the starting material, that test in which the purity of the isoprene is over 99 mol percent, although aluminum chloride dissolved in methyl chloride was used as a catalyst, resulted in a high iodine number; a very high viscosity according to Moonejf, which is a sign of a useful molecular weight in connection with an increased iodine number. The iodine numbers are all between 50 and 175. Likewise, a suitable molecular weight combined with a satisfactory iodine number has been observed for those products made using zirconium tetrachloride organic ether complexes as the polymerization catalyst. If, however, the conventional isoprene of low purity of about 96 mol percent is used when using the conventional polymerization catalysts of aluminum chloride in methyl chloride solution and the starting material contains enough isoprene to give the desired high iodine number, the low Mooney viscosity shows that the usefulness of the polymer is greatly reduced. Products with such a low Mooney viscosity are difficult or impossible to vulcanize into valuable rubber-like products. In all cases the total amount of active catalyst was the same.

The reaction can be carried out either continuously or batchwise. Between the two ways of working, ■ there is little difference with regard to the quality of the polymer, although the method of operation is steady offers certain practical advantages.

To perform a continuous or intermittent process, a Mixture of isobutylene and isoprene produced, in which isoprene to about 25 to 150 percent by weight, based on isobutylene, is included. It is particularly useful to use highly purified starting materials. Isobutylene should have a purity of at least 98% and isoprene of at least 99%, if the customary Friedel-Crafts polymerization catalysts are used. It seems that one is at Use of the customary Friedel-Crafts catalysts not more than about 1% impurities may have. The presence of small amounts of saturated compounds such as propane and butane is likely insignificant, but the presence of propylene, butene-1 or butene-2, pentenes and certain other interfering impurities is undesirable.

The mixture can be polymerized as such. Usually, however, one polymerizes in the presence of one Diluent, which is noticeable for the process itself as well as for the finished end product Offers advantages. '

One or more of the lower halogen-substituted aliphatics, such as ethyl or methyl chloride, methylene or ethylene dichloride, chloroform, the various ethyl chlorides, the various Propylchlori.de, the corresponding fluorides and some of the corresponding Use bromides. Any of the halogen-substituted aliphatics can be used as the diluent, its Freezing point below the polymerization temperature. One can also use carbon disulfide or use low freezing hydrocarbons; here too it is only necessary that the freezing point of the diluent is below the polymerization temperature. In general it is necessary that the substance used as a diluent is liquid at the polymerization temperature is and neither with the unsaturated compounds

696/508

St 4634 IVb / 39 c

still reacts with the catalyst. In general, the requirements for the diluent are The same as for the catalyst solvent in that the diluent is also low Must have freezing point and must not form complexes with the polymerization catalyst. Either before or after mixing, the starting materials are brought to a temperature below about o ° cooled before the polymerization begins.

ίο The preferred temperature range is for the polymerization below 0 °, preferably between about 6o and -10 °, although temperatures are also possible up to —16 / |. ° can be used. The cold one The reaction mixture is fed into a reaction vessel, which can be used either intermittently or continuously Can be designed to work and is surrounded by a cooling jacket. Highly recommended coolant are liquid ethane, which solidifies at -88 °, and liquid ethylene with a solidification temperature of -103 °.

You can also work with internal cooling. In this case it is necessary that the boiling point of the mixture is within the desired range and that the internal coolant is inert and does not react with the polymerization catalyst. Liquid or solid CO ₂ , liquid ethane and liquid ethylene are preferably used as internal coolants.

If highly purified isoprene is used (about 99 ° / _0), the reaction mixture is polymerized by use of a Friedel-Craft's catalyst, contains dissolved in a non-freezing and non-complex-forming solvent which active metal halide. When using highly purified isoprene, aluminum chloride is preferably used as the catalyst. Various other Friedel-Crafts active metal halide catalysts can also be used, e.g. B. aluminum bromide, titanium tetrachloride, uranium chloride, mixed chlorine-bromine halides, especially of aluminum and titanium and chloroalkoxides, especially of aluminum. Due to their low solubility in the olefin material and / or their low rate of dissolution, these catalysts cannot be used in solid form because the solid particles are encased in a very thin layer of initially formed polymer, which further dissolves and prevents further polymerisation. It is essential that the catalyst be in the form of a liquid if one wishes to produce a solid vulcanizable polymer. Titanium tetrachloride is liquid not only at room temperature, but also at such a low temperature that it can easily be incorporated into the mixture of unsaturated compounds. The other catalytically active substances are easily soluble in the catalyst solvents, such as the halogen-substituted aliphatics, in sufficient concentration, in some cases also in the hydrocarbons themselves, in order to achieve excellent catalyst solutions.

To produce isoprene with a purity of 99% and more, the impure material is first freed from peroxide by adding a retarder, then treated with liquid sulfur dioxide at about 50 to 100 °, whereby one. Sulfone wins without the formation of substantial amounts of polysulfones. Thereupon, the resulting sulfone and regenerated is isolated from it isoprene by heating to about 120 to 150 ^0th The resulting product has a purity of 99% and above. However, this cleaning method is not the subject of the invention.

When the desired amount of polymer has formed, the reaction mixture with the therein added polymer contained in warm water to bring the solid polymer to room temperature bring and evaporate the remaining portions of the Pplymerisationsgemisches. The ones that didn't respond separated olefins and diluents can be recovered and reused. The solid polymer is then drawn off as a suspension in water and from this suspension filtered off and dried.

The catalyst can be inactivated with substances such as alcohols, ethers, ketones, amines and ammonia when the reaction mixture is still cold. . After the claimed process one obtains a Copolymer of isobutylene and isoprene, the molecular weight of which (according to Staudinger) is about 20,000 up to 100,000 and its iodine number is 55 to 175. The related viscosity according to Mooney (8 minutes) should be 25 to 60, so that the polymer can be vulcanized satisfactorily can. This specified range is important because polymers of lower molecular weight either not vulcanize at all or vulcanize too slowly to carry out the process on an industrial scale to be able to. On the other hand, there are polymers with higher molecular weights than those specified Area so tough and leathery that it is extremely difficult to process on the roller, although in some cases they can be softened with oil and have a high load of oils and other plasticizers is also effective.

The finished, highly unsaturated polymers and the mixtures are available for use in commerce treated and processed in the known manner.

The examples given below represent a number of particular embodiments of the invention, without the invention being exhausted therein. ,. u ₀

Example 1 .

A number of polymerizable mixtures with varying levels of highly purified Isoprene subjected to polymerization. The percentage of isoprene was 25 to 100 percent by weight, based on the total isobutylene content of the starting material. The isobutylene used had one Purity of at least 96% and isoprene 99% and more. This was 99% isoprene obtained by fractionation of a crude product in which only a small part of the middle course was used. Methyl chloride was used as the diluent, the weight ratio being methyl chloride to isobutylene was a constant 2: 1. In each case, reactants and diluents were

509 696/508

St 4634 IVb 139 c

medium mixed together in a mixing vessel made of stainless steel and is cooled by external cooling to -96 ^{x 0th} The catalyst solution was cooled to -78 ° and added to the stirred mixture of olefinic. Sprayed on reactants and diluents.

The catalyst consisted of a solution of aluminum chloride in methyl chloride, the concentration of which was about 0.24 g of aluminum chloride per 100 ecm of methyl chloride. The different approaches were only partially polymerized, with at least 20% of the starting isobutylene in the polymer in each case were converted.

After the reaction mixture had been worked up in the usual manner, the ■ the mixture specified below was produced, and the properties of the vulcanizates were investigated.

Weight component parts
20th

Polymer 100.0

Zinc oxide 5.0

Stearic acid ...; 3.0

Carbon black 50.0

Mercaptobenzothiazole 1.5

Diphenylguanidine o; 5

Sulfur 2.0

The values for the Mooney viscosity of the polymer. sats and the test results of the vulcanizates are in Table II given.

Example 2

A number of mixtures of commercially available isobutylene-isoprene copolymers (so-called Butyl rubber) and varying amounts of an isobutylene-isoprene copolymer according to the invention produced, which was obtained from an olefinic starting material that is 65 to 150 percent by weight Isoprene, based on the isobutylene content. In general, these were mixtures from a larger proportion of butyl rubber and a smaller proportion of the more unsaturated according to the invention Copolymer produced. In the usual way, those in the following The names given in the table are used to sort the samples according to the composition of their original material to be marked:

Polymer composition
Isobutylene
Parts by weight of the initial goods
Isoprene
Parts by weight A.
B.
C. 100
100
100 65
100
150

Table III shows the behavior of the polymer during extrusion and during flow, the mechanical properties of the vulcanized product are also given. Those mixtures which, in addition to the normal butyl rubber, has smaller proportions of the more unsaturated according to the invention Contain copolymers, have very good processing properties, are quickly vulcanizable and lead to vulcanizates of high modulus. It is particularly noteworthy that the use of polymer during compression to a higher and lower extrusion rate Volume increase leads, measured in g / cm of injected profile. Plus, the mixing just has a lot little effects on the flow behavior. The greatly increased moduli of the vulcanizates are also considerable Advantages of these mixtures.

The mixtures which were used for the extrusion tests and the investigation of the flow behavior consisted of 100 parts by weight of polymer mixture with about 50 parts of carbon black. To test the behavior during extrusion, an extrusion press with an extrusion head and cylinder at 104 ^{0 was} used. To test the flow behavior cylindrically shaped beads were exposed for 3 minutes at 40 ⁰ a load of 1.81 kg / cm ^2, after which the sample is allowed to recover for 20 minutes at 40 ^0th The mechanical properties of the vulcanizate were determined on the following mixture:

Weight component parts

Polymer 100.0

Zinc oxide 5.0

Stearic acid '.. 3.0

Carbon black 50.0

Tetramethylthiuram disulfide 1.0

Mercaptobenzothiazole 0.5

Sulfur 2.0

Example 3 _g5

Table IV contains further test results for mixtures of butyl rubber with the invention Isoprene-isobutylene copolymers made from isoprene-isobutylene with high isoprene content. These values also show the good results, especially the better moduli of elasticity obtained by using the new blends.

Example 4

In Table V, the test results are given on a number of mixtures produced thereby were that 75 to 100 parts by weight of butyl rubber with 25 to ο parts by weight of an inventive highly unsaturated isobutylene-isoprene copolymer mixed. The last-mentioned copolymer was obtained from an initial material which contained equal parts of isobutene and isoprene. Here, too, there is a noticeable improvement in the physical properties of the corresponding vulcanizates can be seen, especially with regard to the moduli.

Table VI shows the behavior of a number of these polymer blends with a high degree of unsaturation towards plasticizers. It can be seen that the behavior of these mixtures Plasticizers with behavior. comparable to butyl rubber alone, in some cases even better than this is.

Example 5

Floor covering panels were produced from two samples, one of which is usual

696 / 50S

St 4634 IVb / 39 c

Butyl rubber of a high degree of saturation and the highly unsaturated isoprene-isobutylene copolymer according to the invention used for the other sample, this product having an actual unsaturation of 8 to 10 ° / ₀ and a Mooney value of 30 to 35.

The composition was as follows:

Weight component parts

Polymer 100.0

Stearic acid 1.0

Zinc oxide 10.0

Sulfur 3.0

'white solid fillers 350.0

Tributoxyethyl phosphate 2.0

Plasticizer 3.0

Tetramethylthiuram disulfide 2.0

Mercaptobenzothiazole 0.75

The test of these two samples for floor covering panels showed that the more unsaturated copolymer was noticeably better than the butyl rubber during vulcanization. This improvement is also due to the fact that it is considerably easier to remove the mold immediately after opening the mold after vulcanization has taken place. A marked improvement in hardness was also noted. The Butylkautschukprodukt had a hardness of 62 to 70 Shore when it was vulcanized 10 to 30 minutes at 163 ^0th The more unsaturated product according to the invention showed a hardness of 84 Shore after vulcanization for 5 minutes at 164 ° and 88 Shore after vulcanization for 10 minutes. In addition, the tests with the butyl rubber show that the elongation has fallen from over 370 to 180%. The vulcanized sheets made from the highly unsaturated copolymer according to the invention also had considerably better elastic behavior.

Table I.

Isoprene,
related to
Isobutylene
in the exit
good, in ° / ₀ . Purity of
Isoprene
in moles
percent Kata
lyser *) viscosity
after
Mooney
(8 minutes) Molecular
Weight
(Traffic jam
things) Mole percent Iodine number,
calculated
out
Unsaturated
Ness attempt
No. Unsaturated
Ness,
tightened
mercury
acetate- 25th 99 *) AlCl ₃ 53 method 55 I. 25th 96 ZrCl ₄ 43 27,700 8.08 55 2 25th 96 AlCl ₈ 18th - - 55 3 3D . 99 *) AlCl ₃ 54 - - 61 4th 3D 96 ZrCl ₄ 34 25,500 9-04 61 5 30th 96 · AlCl ₃ 22nd - - 61 6th 100 96 ZrCl ₄ 40 - - 128 7th 100 .99 ZrCl ₄ 75 - 18.95 **) 128 8th 100 99 AlCl ₃ 67 - - 128 9 100 96 AlCl ₃ 42 - - 128 IO -

*) A1Q ₃ solution containing 0.24 g of AICI3 / 100 cm ^{3 of} methyl chloride;

ZrCl ₄ solution containing 0.32 g of ZrCl ₄ as ZrCl ₄ - (Cl CH ₂ CH ₂ ) ₂ 0/400 cm ^{3 of} methyl chloride.

**) Due to the difficulty of solving the sample, this value is probably no better than an estimated and must probably be higher.

Table II '■ ■ ■

Properties of copolymers from a starting material with a high isoprene content

° / _{0 of} the off viscosity Tensile strength kg / cm ² 20 minutes Vulcanization at 153 ⁰ 20 minutes % Elongation after 10 mins 20 minutes good going on after after vulcanization time 122 73 Vulcanization time 670 480 highly purified Mooney from 145 Module at 300 ° / ₀ elongation 94 from 480. 430 Ver Isoprene, (8 minutes) 10 mins HS in kg / cm ² 98 420 340 search related to 120 HS after vulcanization time - 210 170 No. the isobutylene ΙΟΙ from content of 66 95 10 mins Starting good 60 96 46 II 25th 71 53 12th 33, - 67 13th 40 - 14th 100

509 696/508

St 4634 IVb / 39c

Table III

Mixtures of

(ι) Copolymer of isoprene-isobutylene with a high isoprene content
and (2) butyl rubber.

Extrusion behavior g / cm Look Flow behavior not
recovered Volcanic
station
time Properties of the vulcanizates Module at
300 <y ₀ 1 400%
strain 53 strain
. % Together
settlement
10 cm / min. 0.83 smooth Total-
def. 15.6% 20 ' train
strength
kg / cm ² 34 78 860 Butyl chew 120.7 40.5% 40 215 49 109 750 chuk 80 217 73 650 213 ₁₅ butyl chew 99 chuk O, 8o smooth 15.8 20th 70 120 650 90 pieces 125.7 38.5 40 175 86 126 590 Polymer B, 80 180 9 ¹ 550 10 parts 171 20th
Butyl 106 rubber, 0.76 smooth 12.3 20th 84 - 410 75 parts 137.2 37.0 40 106 89 - 360 Polymer B, 80 105 83 360 25 25 parts 89

Table IV

Mixtures of

(1) Copolymer of isoprene-isobutylene with a high isoprene content
• and (2) butyl rubber

Weight
share Weight Component (1) Mooney
viscosity Volcanic
sation time Properties of the Vulcanizate kg / cm ² 27.8 strain Butyl
rubber share (8 minutes) Minutes tensile strenght Module at
■ 300% 400% 46.2 0 /
/ 0 (2) _ ■ _ IO kg / cm ² 70.7 1030 100 20th l6l, 0 14.7 93.8 890 40 190.8 28.0 36.4 760 80 196.0 43.4 61.6 640 IO 6l IO 193.2 57.4 87.5 960 90 20th l6l, 0 23.8 109.9 850 40 I87.3 39.2 5i, i 730 80 197.8 58.8 81.9 650 IO 56 IO 197.8 74.2 95.9 840 " , 90 20th '127.8 . 35, o 102.2 660 40 145.3 57.4 52.5 ' 650 80 159.3 67.2 81.2 ' 620 IO 64 IO 155.8 70.7 86.1 800 90 20th 117.3 37> i 84.7 670 40 136.5 57.4 53.9 640 .80 140.0 61.6 84.7 620 IO 35 IO 129.5 ^s 58.5 99.4 780 90 20th 131.3 35.7 100.1 660 40 150.5 59.5 51.1 600 80 155.8 67.2 78.4 590 IO 79 IO 145.3 68.6 94.5 800 90 20th 141.8 32.2 104.3 '70O 40 . 157.5 53.2 650 80 164.5 63.0 610 l6l, 0 70.7 designation
of the poly merisats _ A. B. C. B. B.

St 4634 IVb 139 c

Table V
Properties of copolymer B / butyl rubber mixtures

Weight
share Weight Vulcanization time
Minutes Mechanically! ; Properties of the vulcanizate 1 at
400% Elongation ° / ₀ Butyl
chew
chuk share
Poly
merisat B ■ 5 tensile strenght
kg / cm ² Modt
3 ° o%
kg / 23.8 960 IOO _ IO 105.0 14.0 53.9 780 20th 136.5 35, o 82.6 630 40 127.8 58, i 105.0 470 .5 115.5 78.4 48.3 740 95 5 IO 105.0 33.6 82.6 630 20th 124.3 58.1 109.2 510 40 129.5 54, o 117.6 430 5 127.8 89.6 51.8 670 90 IO IO 89.3 37, i 82.6 550 20th 106.8 58.8 98.0 470 40 110.3 73.5 104.3 450 5 112.0 80.5 44, i 520 75 25th IO 50.8 36.4 57.4 430 20th 59.5 49, o - 39 ° 40 57.75 49, o - - - -

Table VI

Behavior of copolymer B / butyl rubber mixtures
against plasticizers *)

Butyl Polymer Soft- Extrusion behavior cm / min. g / cm ' Look Flow behavior Duration Total- not rubber B. making oil the def. / recovered Weight Weight Weight 123.2 0.84 smooth load % % share share share Minutes 32.8 7.7 129.5 o, 88 smooth I. 45.1 21.0 IOO 3 46.4 21.3 121.9 0.80 smooth I. 58.2 40.0 IOO - IO 3 27.7 6.7 138.4 0.79 smooth I. 39.5 16.9 90 IO - 3 41.8 15.5 I. 54.8 34.7 90 IO IO 3

*) 50 parts of carbon black were added to the samples.

Claims (2)

Claims ·. i. Process for the production of copolymers seeds of a molecular weight above 20,000 and 55 has an iodine number of 55 to 175 by reacting isobutylene and a conjugated diolefin of 5 to 8 carbon atoms, e.g. B. isoprene, at 0 to 164 ⁰ in the presence of a Friedel-Crafts metal halide catalyst, which is in a solution 60 medium is dissolved from low freezing point, that characterized in that a starting mixture is used which contains 25 to 150 parts by weight of diolefin of a purity of at least 99 mole percent per 100 parts by weight of isobutylene. 2. Embodiment of the method according to claim i, characterized in that as a catalyst a zirconium tetrachloride ether complex as a solution in a solvent of low Freezing point is used. © 509 696/508 2. 56