DE1915237C2 - New polymers containing sulfonated aromatic rings and processes for their preparation - Google Patents

Description

R ₃ R ₃

are used, in which A, B and C independently represent oxygen or -CH2- and Ri, R2 and R3 independently represent Ci-Cio-alkyl, -aryl, -alkaryl or -aralkyl.

8. The method according to claim 2, characterized in that the Lewis bases are organic pyrophosphates the general formula

R ₁ R ₂ R ₃ R ₄ P ₂ O ₇

- are used, in which R ₁ , R2, R3 and R _{4 are} independently hydrogen, C1-C12-alkyl, -aryl, -aralkyl, -alkaryl or their substituted derivatives, but at least two radicals R are not hydrogen.

9. The method according to claims 2 to 8, characterized in that the molar ratio of the SO; rDonators to the Lewis base is 1: 1 to 15: 1.

10. The method according to claims 2 to 9, characterized in that the molar concentration of the SOi complex in the reaction medium is 3: 1.

11. The method according to claims 2 to 10, characterized in that the molar ratio of the Sulfur trioxide donor to complexing agent is about 1: 1 to 9: 1.

The invention relates to sulfonated, aromatic ring-containing polymers based on styrene-butyl rubber graft copolymers, homogeneous styrene-isobutylene copolymers, styrene-butadiene copolymers or styrene-acrylonitrile copolymers in which the sulfonic acid group is neutralized, and a process for their manufacture.

Ionic polymers are crosslinked, but they have a melting point or softening point or Softening range and can even be dissolved in various solvents. With normal At service temperatures, these ionic polymers behave in a similar way to crosslinked polymers. At increased However, they are easily deformed at temperatures and in the same way as thermoplastic ones Processing and processing resins. These ionic polymers (ionomers) owe their unique properties the fact that the crosslinking occurs through ionic and not through covalent bonds between molecules of the polymer has been effected. Copolymers of ethylene are typical of these ionic polymers and ethylenically unsaturated mono- or dicarboxylic acids which have been neutralized by metal salts (See e.g. British Patent 1011981 and USA Patent 3264272).

By copolymerizing a styrene sulfonic acid salt and other monomers, sulfonic acid ionomers are made has been produced, forming plastic polymers which contain ionic crosslinking bridges. In this process, described in US Pat. No. 3,322,734, acid-modified monomers are used assumed that are exclusively polymerized. This polymerization already takes place considerable networking takes place.

Sulfonated polymers containing aromatic rings based on styrene-butyl rubber graft copolymers, homogeneous styrene-isobutylene copolymers, styrene-butadiene copolymers or styrene-acrylonitrile copolymers, in which the sulfonic acid group is neutralized, as well as processes for the preparation thereof Polymers are known from US Pat. No. 3,072,618. This is a complex of a lower alkyl phosphate with SOi used as a sulfonating agent. This creates a sulfonation process that is related to the side reactions can be easily controlled and the production of essentially uncrosslinked products permitted. The sulfonated products are thickeners for aqueous systems, impregnating agents, Binders, soil improvers and textile layers. According to the teaching of this publication Olefins, aromatics and polymers with alkylene aromatic groups can be sulfonated, whereby because of which - despite the mild conditions - high degree of sulfonation water-soluble products are obtained.

According to US Pat. No. 3,072,619, water-soluble products are obtained in a similar manner.

The object of the present invention is to provide polymers with improved mechanical properties and a To create a process for their preparation, the copolymers obtained after neutralization are ionically crosslinked and have elastomeric properties.

This object is achieved by the features in the characterizing part of claims 1 and 2.
The tensile strength, Young's modulus, and high temperature melt strength can be further improved in the present invention.

In particular, elastomeric polymers containing aromatic rings can be converted by the Polymers with a sulfonation agent containing about 1 to 4 moles of sulfur trioxide and about 1 mole of a complexing agent contains, are sulfonated. Suitable complexing agents are Lewis bases, oxygen, phosphorus or Contain nitrogen. The polymer thus formed can be neutralized with metal salts, amines or Amine derivatives are ionically crosslinked.

To the"'; For a better understanding of the description, reference is made to the accompanying figures. Here Fig.I shows a correlation between the Young's modulus in dynes / cm ² and the content of SO3H or ionic constituents in a homogeneous styrene-isobutylene copolymer, while in Fig.II the tensile strength of a styrene-isobutylene copolymer of sulfonated polymers and their corresponding ionic polymers as a function of temperature.

The term "butyl rubber" as used herein includes copolymers obtained from a polymerization reaction mixture be prepared, the 70 to 99.8 wt .-% of an isoolefin having about 4 to 7 carbon atoms,

z. B. isobutylene, and about 30 to 0.2 wt .-% of a conjugated, polyunsaturated olefin with about 4 to 14 carbon atoms, e.g. B. isoprene contains. The copolymer obtained contains 85 to 99.8% by weight of bound isoolefin and 0.2 to 15% bound polyunsaturated olefin.

Butyl rubber generally has a Staudinger molecular weight of about 20,000 to 500,000, preferably about 25,000 to 400,000, in particular about 100,000 to 400,000, and a Wijs iodine number of about 0.5 to 50, preferably 1 to 15. Production of butyl rubber is described in US Pat. No. 2,356,128.

For the purposes of the invention, a butyl rubber is preferred which is about 0.5 to 6%, preferably 0.5 to 3% e.g. B. 2%, bound polyunsaturated olefin contains.

The first stage in the production of butyl rubber ionomers is the grafting of styrene onto the butyl rubber main chain. The grafting takes place by halogenation of the butyl rubber and then Reaction with cationically polymerizable monomers (e.g. styrene) in the presence of an aluminum alkyl or haloaluminum alkyls as a catalyst. The graft polymer is then complexed with sulfur trioxide reacted with a Lewis base to sulfonate the aromatic ring. The polymer then becomes converted into an ionomer by neutralization of the sulfuric acid component.

Halogenated butyl rubber is commercially available and can be made as follows: butyl rubber is in a solution containing 1 to 60 wt .-% butyl rubber in an essentially inert Cs-Cs hydrocarbon contains as a solvent such as pentane, hexane, heptane, etc., halogenated. This butyl rubber cement is treated with a halogen gas for about 25 minutes, with halogenated butyl rubber and a Hydrogen halides are formed. The copolymer contains up to 1 halogen atom per double bond in Copolymers. The production of halogenated butyl rubbers has long been known (see for example U.S. Patent 3099644). The invention is in no way limited by the manner in which Butyl rubber is halogenated. Both chlorinated and brominated butyl rubber are for the purpose suitable for the invention.

A chlorinated butyl rubber is representative of commercially available halogenated butyl rubbers Contains 1.25% by weight of chlorine and 2 mol% of unsaturated units and an average value determined from the viscosity Has a molecular weight of about 357,000.

The production of butyl rubber-styrene graft polymers from halogenated butyl rubber is described in Belgian patent 701850.
The ionomer formed from the graft polymer is believed to have the following structure:

CH ₃ CH ₃ H

(CH ₂ -Ο
ι ~ (CH ₂ -C) = CH-O- · butyl main chain
ι I.
CH ₃ I.
CH ₂
I. Hc- ^ o y CH ₂
I. HC- <fOy CH ₂ HC - (^ oV-SOj "' CH ₂

Herein M * is preferably a group I metal ion. Group II, III, IV, V, VIb, VIIb and elements VIII of the Periodic Table can also be used.

The process described is based on the formation of sulfonationomers from any polymer that has a aromatic ring contained in their structure, applicable. This is a particularly suitable polymer homogeneous styrene-isobutylene copolymers of the general structure:

CH ₃

CH ₃ H

-CH ₂ -C-CH ₂ -C-CH ₂ -C

CH ₃ / \ CH ₃

The term "homogeneous" is used to distinguish this polymer from more common styrene-isobutylene copolymers, which are predominantly polymer blends of polystyrene and polyisobutylene.

These homogeneous polymers can be maintained by continuous solution polymerization of the steady state in a reaction vessel with good mixing. as Solvent for the polymerization is either hexane or a hexane-rich mixture of hexane using Methyl chloride used. The polymer can contain 0.5 to 90 mole percent styrene. For the purpose of education of ionic polymer, the polymer contains about 2 to 80 mol% styrene. The lowest degree of sulfonation for minimal solubility in polar solvents corresponds to about 7 moles of styrenesulfonic acid groups per 100 monomer units in the copolymer. The highest degree of sulfonation for achieving good thermal and mechanical stability is about 60 moles of sulfonated styrene groups per 100 moles of monomer units Copolymers.

Further polymers which can be sulfonated by the process according to the invention are copolymers of styrene and butadiene, styrene and isoprene, chloroprene and styrene, acrylonitrile and styrene (SAN), and styrene Acrylic acid, graft polymers of styrene on polybutadiene, graft polymers of styrene-acrylonitrile copolymers (SAN) on polybutadiene (ABS), styrene-isobutylene-isoprene terpolymers, etc.

A typical sulfonation process consists in ^{bringing the polymer into contact with a sulfonation complex at about 0 to 100 °} C. for a period of a few seconds to several hours, which is preferably made by reacting about 2 to 4 mol of sulfur trioxide with 1 mol of a phosphorus compound and the sulfonated polymer is isolated.

In the method according to the invention, a polymer containing alkenyl aromatics is treated with a sulfonating agent sulfonated, which uses a sulfur trioxide donor in combination with a Lewis base as a complexing agent contains. In the preferred embodiment, the Lewis base is a trialkyl lower phosphate used.

The term "sulfur trioxide donor" used here refers to substances including SO3 that Contain sulfur trioxide in a loosely bound form from which it can be easily released.

Examples of sulfur trioxide donors which are suitable for the purposes of the invention are sulfur trioxide, fuming sulfuric acid (oleum, 20 to 80%), chlorosulfonic acid and fluorosulfonic acid. This here The term used "complexing agent" denotes the Lewis base which is suitable for the purposes of the invention are.

The term "Lewis base" as used here refers to materials that have electron pairs below Release formation of covalent bonds. The term includes the known Lewis bases as well as others Complexing agents that act as Lewis bases in the sulfonation reaction.

In a preferred embodiment, the base and available sulfur trioxide are prior to Mixing together with the polymer (to form a complex). However, it is not It is essential that the available sulfur trioxide is premixed with the complexing agent, rather it is only necessary that the complexing agent is present during the sulfonation reaction. For example the available sulfur trioxide and the complexing agent can be used simultaneously with the organic substance and the complex can be formed in situ in the sulfonation zone.

Since the complexing agent affects the reactivity of the available sulfur trioxide, which does not need sulphonation temperature below 0 ° C to be held, but they can range from -100 ⁰ C to 100 ⁰ C vary. Furthermore, the pressure is not a critically important factor, rather the pressure can be adjusted to any suitable value. For example, the sulfonation can be carried out in a reduced pressure range of, for example, about 0.5 atm. up to an overpressure of about 10 atm. be performed. From an economic point of view, it is most expedient to ^{carry out the reaction at temperatures from 15 to 40 °} C. and approximately at normal pressure. The sulfonation time is of course different depending on the particular conditions chosen, the compounds to be sulfonated and the complex used. In general, the reactions are completed in a time from a few seconds to several hours after the reactants are brought together. If sulfonation is carried out at room temperature and normal pressure, the contact time should be about 5 seconds to 25 or 30 minutes. Since the complexing agent reduces the activity of the sulfur trioxide, it is not necessary to limit the sulfonation time, as is necessary in conventional processes. This also applies to the cleaning stage, where it is desirable to keep the organic substance in contact with the sulfonating agent for a few hours.

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Certain phosphorus compounds are representative of Lewis bases that are suitable as complexing agents. The }·.;

Phosphorus compounds can be inorganic or organic, but organic phosphorus compounds;.;

bonds of the general formula jfi

R ₁ \ A. \ or Ri \ A. \ B-P (O) - Β — Ρ - R ₂ R ₂

R ₃ R ₃

preferred, in which A, B and C independently represent oxygen or -CH ₂ - and Ri, R ₂ and Rj are independently selected from the group C1-C20-alkyl, -aryl, -alkaryl or -aralkyl. A wide variety of organic phosphites, phosphinites, phosphinates, phosphates, phosphonates, phosphonites and phosphines can be used as complexing agents.

Phosphoric acid, phosphorous acid, Pyrophosphoric acid, metaphosphoric acid, phosphonic acid and phosphinic acid. Besides the acids can also their mono-, di- and trisubstituted derivatives can be used. Preferred as phosphorus compounds are however the trialkyl phosphates and phosphites.

Other organic phosphorus compounds that are suitable as complexing agents are, for example, triethyl phosphate, Trimethyl phosphate, tripropyl phosphate, tributyl phosphate and triethyl phosphite.

The organic compounds which are suitable as complexing agents also include the organic ones Pyrophosphates. These compounds have the general formula

RiR ₂ R ₃ R ₄ P ₂ O ₇

Here, Ri, R ₂ , R3 and R _{4 are} independently selected from the group consisting of hydrogen, Ci-Ci ₂ -AlKyI, -aryl, -aralkyl,

-Alkaryl and mixtures thereof are selected, but at least two radicals R not being hydrogen. the R radicals can be halogen-substituted. In the case of phenyl radicals, the radical R can be halogen or nitro substituted be. When the term "substituted derivatives" is used with reference to these radicals R, then These are to be understood as meaning nitro- or halogen-substituted radicals R.

Examples of these organic pyrophosphates are tetraethyl pyrophosphate, tetramethyl pyrophosphate, Dimethyl diethyl pyrophosphate and bis (2,4-dichlorophenyl) diethyl pyrophosphate. When using pyrophosphates may have up to 15, but preferably 12, moles of available sulfur trioxide with each mole of the phosphorus compound be complex bound.

Lewis bases which contain oxygen or nitrogen are also suitable as complexing agents.
The nitrogen-containing Lewi 'bases which form active complexes with sulfur trioxide donors and are suitable for the sulfonation of the unsaturated polymers according to the invention have the general formula

Here, Ri, R ₂ and R3 are independently hydrogen or Ci-C36-alkyl, -aryl, -alkaryl, -aralkyl or mixtures thereof, with the proviso that in cases in which Ri and R _{2 are} hydrogen, R3 is not hydrogen may, and R _{4 is} a C3-C36 alkylene radical. Any primary, secondary or tertiary organic amines or cyclic organic amines can be used as nitrogen-containing Lewis bases. If the radicals Ri, R ₂ , R3, R ₄ or R5 contain more than two carbon atoms, they can be heterogeneous organic radicals which contain oxygen, chlorine, nitro groups or mixtures thereof. In other words, Ri, R ₂ , Rj, Ri and R ₅ can be ether groups, contain substituted halogen atoms and nitro groups, or comprise both ether groups and substituted groups. With regard to Ri, Rj, R3, Ri and R5 in these formulas, the term "substituted analogs" used here means the radicals R described and substituted with the abovementioned substituents. For the purposes of the invention, the radicals Ri, R ₂ , R3 fall , R ₄ and R5 in cases in which they are ether groups, in the class of "substituted analogs". In cases in which Ri, R ₂ and Ri contain aryl, alkaryl or aralkyl radicals, the use of the sulfur trioxide donor in excess is necessary in order to compensate for any sulfonation of the aromatic units.

Examples of these nitrogen-containing Lewis bases are trimethylamine, triethylamine, dimethylaniline, diethylaniün, Piperidine, morpholine, N-ethylmorpholine, diethylaminoacetate and 2-chlorotriäthylamine.

R ₂ -N or R ₄ N

IFl

Further suitable complexing agents which contain nitrogen can be given by the formula
R ₃

are shown, in which Ri, R2, R3, R4 and Rs stand for hydrogen, halogen or Ci-C36-alkyl, -aryl, -alkaryl or -aralkyl. In cases where Ri, R2, Rj, R4 and R5 contain aromatic units, it is necessary to use the sulfur trioxide donor in excess in order to achieve a ?. To compensate for sulfonation of these units. The organic radicals R ₁ , R 2, R3, R4 and R5 can contain halogen atoms, oxygen atoms or nitro groups. In relation to these R radicals, the term “substituted analogs” used here means the R radicals described which are substituted with oxygen or halogen or which contain oxygen in the carbon chain. Also, structures of fused cyclic rings and polymer structures are suitable.

Examples of this type of compound are pyridine, 2-methylpyridine, 2,6-dimethylpyridine, quinoline, quinaldine and poly-2-vinyl pyridine. Triethylamine and tri-n-propylamine are preferred as nitrogen-containing complexing agents. The molar ratio of the sulfur trioxide donor to nitrogen in the complex can be up to 5: 1, however, a ratio of 1: 1 is preferred.

Chlorinated hydrocarbons are suitable solvents for the production of these complexes. the The concentration of the complex in the solution is preferably 5 to 20% by weight, in particular 10 to 15% by weight. The complexes can also be formed by direct addition of the reagents, if for this Care is taken that the heat developed is dissipated. The reactions of complexes of SO3 with Molecules that contain nitrogen and the polymer backbones that contain aromatic rings prove to be non-quantitative. It is therefore advisable to use an excess of the complex in these reactions use.

Oxygen-containing Lewis bases proved to be advantageous for the complex binding of the sulfur trioxide donor, to facilitate the reaction with the unsaturated units of the polymer molecules. These bases have the following general formulas

Rl O

O or R ₃ O or OO

K2

Here, Ri and R ₂ independently of one another represent C2-C36-alkyl, -aryl, -alkaryl or -aralkyl and R3 represents C3-Ci6-alkylene. R ₃ can be a substituted alkylene radical. The substituents can be Ci-C2o-alkyl, -aryl, alkaryl or -aralkyl. If the radicals Ri, R2 or R3 contain more than two carbon atoms, halogen, nitro groups and ether oxygen atoms can also be present. With respect to Ri, R2 and R ₃ , the term "substituted analogs" used herein means R3-substituted as described above. The presence of aryl, alkaryl or aralkyl radicals in the base requires the use of excess SO3, since part of the SO3 is consumed in the sulfonation of the aromatic groups.

Representative examples of oxygenated Lewis bases suitable for the purposes of the invention, are tetrahydrofuran, p-dioxane, 2,3-dichloro-1,4-dioxane, m-dioxane and 2,4-dimethyl-1,3-dioxane.

Further oxygen-containing Lewis bases which are suitable as complexing agents are esters of the general formula

O Il

R ₁ -COR ₂

in which Ri and R _{2 are} Ci-Cio-alkyl radicals, phenyl or benzyl radicals. Examples of such esters are benzyl acetate, butyl acetate, butyl propionate, methyl benzoate, hexyl acetate, isobutyl benzoate, ethyl o-bromobenzoate, p-nitrophenyl acetate, ethyl n-butyrate, ethyl stearate and ethylphenyl acetate.

The molar ratio of SCb donor to base can be up to 15: 1 and is preferably about 9: 1 up to 1: 1, in particular about 5: 1 to 1: 1. Particularly preferred is a molar ratio of about 2: 1 to 4: 1, e.g. B. 3: 1.

As a solvent for the preparation of the complexes of the sulfur trioxide donor with complexing agents that Contain oxygen, are preferably chlorinated hydrocarbons or the oxygen-containing complexing agent used. Examples of such chlorinated solvents are carbon tetrachloride, dichloroethane, Chloroform and methylene chloride. The complexes can also be formed by direct addition of the reagents if care is taken that the heat generated is dissipated.

The reactions of ether complexes of SO3 with the polymer chains containing aromatic groups, turned out to be non-quantitative. Therefore, it is desirable to use the complex in excess to achieve the required degree of sulfonation.

Any phosphorus, oxygen or nitrogen-containing Lewis bases can be used alone or as a mixture Complexing agents can be used. The organic phosphorus compounds are preferred as complexing agents.

When using the phosphorus-containing complexing agent, the complex can contain about 1 to 15 moles of sulfur trioxide donor contained per mole of complexing agents. About 1 to 9 moles are preferred, in particular about 1 to 5 moles. Particularly preferred are 2 to 4 moles, e.g. B. 3 moles.

The preferred complexing agents are trimethyl phosphite, triethyl phosphite and triethyl phosphate used. The latter is particularly preferred. SO3 is preferred as the sulfur trioxide donor.

To carry out the method according to the invention, the polymer to be sulfonated is in a suitable IC th solvent and dissolved with a complex that contains the complexing agent and the sulfur trioxide donor contains, implemented at moderate temperatures. The solvent must be both the polymer and the Solve complex. Preferably a non-aromatic solvent is used. Examples of such Solvents are alkanes, chlorinated alkanes, ethers, esters and their mixtures. The alkane can be linear, branched or be cyclic. Examples of such alkanes are hexane, pentane, butane, cyclohexane, heptane and their Homologues and analogues. Examples of chlorinated alkanes are methyl chloride, ethyl chloride, dichloroethane, Chloroform, methylene chloride, carbon tetrachloride, or any higher alkanes or chlorinated alkanes.

Suitable ethers and esters are, for example, tetrahydrofuran, p-dioxane, diethyl ether, amyl ethyl ether, Bis-penta-chloroethyl ether, bis - /? - chloroisopropyl ether, butyl acetate, isoamyl acetate and cyclohexyl acetate.

The solids content of the polymer solution is preferably below 25% by weight, in particular from about 5 to 20% by weight. A solids content of approximately 10 to 20% by weight is particularly preferred. Pastes can be used with high solids content of up to 60% by weight can be used, but the high viscosity results in a handling problem.

The complex may be preferably formed at about -100 to +100 ⁰ C, at about -40 to +40 ⁰ C. Preferably the complex is formed immediately prior to use. It was also found possible to form the complex in situ in the polymer solution. If the complex is formed before use, its concentration in the solvent should be about 0.5 to 25% by weight. This concentration is preferably about 1 to 20% by weight, with a concentration of 10 to 20% by weight, e.g. B. 18 wt .-%, is particularly preferred.

Sulfonation of the polymer is carried out at a temperature between -100 and +100 ⁰ C. The sulfonation takes place when the complex is added in solution to the polymer solution. The reaction time can be 5 seconds to 3 hours. The product remains soluble during the entire reaction time. It is best isolated by evaporating the solvents in hot water. The water also breaks down the unreacted complex.

The sulfonated polymers can, if necessary, by kneading in the presence of low-boiling Ketones or alcohols are further purified. Acetone and methanol are preferred for this purpose. After kneading, the polymers are dried on a hot roller mixer. The products obtained are soluble in a wide variety of solvents, a sign that sulfonation takes place without crosslinking is done.

Representative of the sulfur trioxide complex that is formed by reacting a complexing agent with SOi is the trialkyl phosphate SOs complex shown in equation (1):

R-O R-O

(1) R - O - P - »O + XSO 3 - f R - O - P -> O: (SO ₃ ); c

R-O R-O

Here, R is an alkyl radical and X is the number of moles of SO3 per mole of phosphorus compound. X preferably has a value of about 1 to 7, in particular about 2 to 4, for example 3.
A typical sulfonation reaction proceeds as follows:

(2) ~ CH ₂ -C - CH ₂ -CH ^ + (RO) ₃ PO: (SO ₃ ) ₃ -

- + (RO ₃ POr (SOj) ₂

CH ₂ -C-CH ₂ -CH

The metal ions which are suitable for the preparation of the ionic copolymers according to the invention, can be divided into two groups: non-complex-bound metal ions and complex-bound metal ions Metal ions. In the case of the non-complex-bound metal ion, the valence of the ion corresponds to the valency of the metal. These metal ions are obtained from well-known and used metal salts.

The complex metal ions are those in which the metal is attached to more than one salt group type is bound, wherein at least one ion is ionized and one ion is not ionized. Since the formation of ionic polymers only require an ionized valence, such complex metal ions are just as good for that Purposes of the invention suitable The suitability of complex metal ions necessary for the formation of ionic Copoiymeren are used, corresponds in terms of their ionized valences to those of the non-complex-bound Ions. The monovalent metals are of course excluded, but the higher valued metals can Metals depending on how many metal ions are complexed and how many are ionized can be included. Complex metal ions in which all metal valences are preferred are preferred except one are complex-bound and one is easily ionizable. In particular, the metal salts of very weak acids, e.g. B. stearic acid, and ionized acids, e.g. B. formic acid and acetic acid are used will.

Suitable non-complex-bound metal ions for the production of ionic copolymers according to the invention are mono-, di-, tri- and tetravalent metals in groups I, II, III, IV, V, VIB, VIIB and VIII of the Periodic Table (see Sect . Page B-3 of Handbook of Chemistry and Physics, Chemical Rubber Publishing Co., 47th Edition). Suitable monovalent metal ions are Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ and Cu ⁺ . Suitable divalent metal ions are Be ⁺² , Mg ⁺² , Ca ⁺² , Sr ⁺² , Ba ⁺² , Cu ⁺² , Cd ⁺² , Hg ⁺² , Sn ⁺² , Fe ⁺² , Pb " ² , Co ^{+ 2} , Ni ⁺² and Zn ⁺² . Suitable trivalent metal ions are Al ⁺³ , Sc ⁺³ , Fe ⁺³ and Y ⁺³ . Suitable tetravalent metal ions are Sn ⁺ ", Zr ⁺⁴ , Ti ⁺⁴ and Pb ⁺⁴ .

In addition to the metal ions, other basic materials, e.g. B. primary, secondary and tertiary amines, can be used for the formation of ionic bonds. The preferred amines have a basicity constant K _b of more than 10 " ^3. The basicity constant can be expressed as de.i.

[Product]

K =

[~ SO3H] [amine]
for the reaction ~ SO3H + amine> product can be defined. Mean therein

[Product] = concentration of the product

[~ SO3H] = concentration of sulfonic acid groups in the polymer

[Amine] = concentration of the amine.

The preferred amines have a ÄVWert in the range of 10 ^-3 to about 1O ^+6, preferably about ³ to 10 IO '. ² Examples of such amines are anhydrous piperazine, tri-n-propylamine, triethylamine and triethanolamine. The secondary and tertiary amines, in particular piperazine and tri-n-propylamine, are particularly preferred.

Because the SOjH groups are side groups of either the aromatic ring or the polymer backbone their concentration in the polymer is in mol%, based on the polymer and not on the aromatic Units, expressed. It is desirable that the sulfonated styrene-butadiene rubber according to FIG Invention about 0.08 to 20 mol% SO3H groups, preferably about 1 to 20 mol%, in particular about 0.5 to 12 mole percent, with about 3 to 8 mole percent, e.g. B. 3.0 mol%, are particularly preferred. About 1 to 100% of the SO3H groups can be neutralized to form the ionomer.

In the case of trivalent metal ions [M ⁺² ] such as Zn ⁺² , Ca ⁺² , Cu ⁺² and Ba ⁺² , the ion content is preferably less than about 12 mol [M ⁺² (styrene sulfonate) 2] groups per 100 monomer units. In the case of trivalent metal ions [M ⁺³ ] such as Al ⁺³ , Fe ⁺³ and Co ⁺³ , the ion content should preferably be less than 1.0 mol [M ⁺³ (styrenesulfonateb] groups per 100 monomer units).

50 Example 1

A homogeneous styrene-isobutylene copolymer was produced in a conventional overflow reactor. Of the The reactor contained a central chamber with a stirrer and two outer chambers for circulating the reactants. The reactor was hung in a constant temperature bath. Two feed lines were used, one for the monomers dissolved in a solvent and the second for the dissolved catalyst. Both feedstocks were precooled to the correct temperature.

The reaction temperature was -90 ⁰ C and the reaction time 30 minutes. The starting monomers consisted of 40% by weight styrene and 60% by weight isobutylene. The monomers were diluted with a mixture of methyl chloride and hexane (60:40) to a concentration of 17.5%. AICI3 was used as the catalyst in a concentration of 0.12% by weight.

After a reaction time of 30 minutes, the activity of the catalyst was increased by adding it to lospropyl alcohol destroyed. The copolymer was isolated and dried. The intrinsic viscosity was 1.099 (1 g / l Toluene at 25.84 ° C). The copolymer had a viscosity average molecular weight of 330,000. A styrene content of 39.3% by weight was determined by nuclear magnetic resonance spectroscopy.

The product had poor strength properties as shown by the values in Table I and was in certain Soluble in non-polar solvents such as benzene and carbon tetrachloride, but did not swell in polar ones Solvents such as alcohol or water as shown by the values in Table II.

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Example 2

The product obtained according to Example 1 was sulfonated according to the method of US Pat. No. 3,072,618. 20 g of polymer were dissolved in 760 ml of dry dichloroethane. 100 ml of a solution of 3.35 ml of triethyl phosphate with 2. + 8 ml of freshly distilled sulfur trioxide in dichloroethane were added to the solution. The reaction time was 10 minutes at 10 ⁰ C. The polymer contained 7.12 x 10 ^"4 equivalents SCBH / g (about 4.9 mol% sulfonated styrene, based on the copolymer).

The physical properties of the copolymer are in Table I and its solubility properties in Table II given.

Table I.

Skill properties of sulfonated homogeneous styrene-isobutylene copolymers at 25 ° C (pulling speed 12.7 cm / minute)

Material *) tensile strenght Swelling in% by volume 300% modulus strain (Example) kbar kbar % I. Styrene-isobutylene copolymer 1930 3.5 1900 Il 4.9 mole percent ~ SO ₃ H 5 950 12.5 1 100 III 4.9 Moi-% ~ SOrNa ⁺ 5 250 27.3 750 IV 13.3 mole percent ~ SO ₃ H 10 300 46.6 500 V 18.1 mole percent ~ SO ₃ H 9 450 32.7 580 VII 13.1 mole percent ~ SO ₃ H ⁺ 7,000 29.4 510 5 mol% Zn (~ SOr) ₂ VIII 20.1 mole percent ~ SO ₃ H 6 510 32.4 440 IX 10.7 mole percent ~ SO ₃ H ⁺ 10 100 77 380 10 mol% Zn (~ SOr) ₂ *) unfilled Table II Behavior ' of sulfonated homogeneous styrene-isobutylene copolymers versus polar and non-polar Solvents (at 25 ° C) Benzene tetrachloro methanol water hydrocarbon material (Example)

0
226

4.2

soluble
soluble
soluble

soluble
soluble

17.3

3.3

97.4

191.6

170

150.5 58.9

I styrene-isobutylene copolymer soluble soluble

II 4.9 mol% ~ SO ₃ H soluble soluble

III 4.9 mol% ~ SO ₃ -Na ⁺ soluble 923

IV 13.3 mole percent ~ SO ₃ H 170 307

V 18.1 mole percent - SO ₃ H 13.9 50.8

VII 13.1 mol% ~ SO ₃ H + 22.0 62.1
5 mol% Zn (~ SOr) ₂

VIII 20.1 mole% ~ SO ₃ H 17.6 48.6

IX 10.7 mole% ~ SO ₃ H + 29.6 89.9
10.0 mol% Zn (~ SOr) ₂

Example 3

The product of Example 2 was converted to an ionic interpolymer by exact equivalents were kneaded by sodium methoxide. Methyl alcohol was driven off by heating. The material is easy to process, press and spray and process again. The strength properties were good (Table I). The product showed similar solubility properties as the product described in Example 2 (see Table II).

Example 4

The product obtained according to Example 1 was sulfonated (according to the general procedure described in Example 2), a product being obtained which contained 1.93 × 10 ° equivalents of SO ₃ H / g of polymer.

determined by titration (see Example 2) and elemental analysis for sulfur. This corresponds to 13.3 mol% sulfonated Styrene units, based on the monomer. The material has excellent strength properties (see Table I) and a wide temperature range in which it is rubber-like. It can be classified under PreC and Apply again easily to spraying conditions (138 ° C, pressure 12 kbar). The material has increased durability to non-polar solvents and reduced resistance to polar solvents s (Table II).

Example p

The material prepared according to Example 1 was sulfonated in the manner described in Example 2, wherein a product having 18.1 mol% sulfonated styrene units was obtained. This product was very strong and elastic (Table I) and could be processed again under pressing and spraying conditions. It was something resistant to non-polar solvents, but was strongly attacked by polar solvents (see Table II).

Example 6

The product described in Example 5 was converted into an ionic interpolymer by exactly equivalent amounts of sodium methoxide were kneaded. The product was difficult to process. Apparently an upper limit for the ionic character has just been exceeded.

Example 7

The product described in Example 5 was converted into an ionic interpolymer by converting ZnO into was added in such an amount that 5 mole percent sulfonated styrene was rendered ionic. The product was easy to process and processable again under pressing and spraying conditions (138 ° C., pressure 12 kbar). That Product had very good strength properties (Table I) and had good resistance to non-polar Solvents (Table II).

Example 8

The product prepared according to Example 1 was sulfonated in the manner described in Example 2, wherein a product having 20.1 mol% sulfonated styrene units was obtained. The product had good handicraft properties (Table I) and was processable again. The material became light with non-polar solvents swollen and was severely attacked by polar solvents (Table II).

Example 9

The product prepared according to Example 8 was converted into an ionic interpolymer by adding ZnO was added in an amount such that 10 mole percent sulfonated styrene was rendered ionic. The product was easy to process and processable again under pressing and spraying conditions. It was made by non-polar Solvent only slightly swollen.

Example 10

In the manner described in Example 2, a styrene-isobutylene copolymer was sulfonated to different degrees. The module was based on sulfonated samples both before and after the preparation of ionomers determined in the manner described in Example 3.

Fig. I shows the influence of hydrogen bonding and ionic bonds on the module. Fig. Ia shows that the modulus increases slightly with increasing content of SOjH groups (mol%). In contrast, will by converting the product into ionomers, the modulus is sharply increased. For example, Fig. Ib a Sample of a styrene-isobutylene copolymer which contains about 16.15 mol% SO3 and is converted into an ionomer with different Degree of ionic crosslinking is converted. Surprisingly, the module changes a lot strong with the ion content.

Fig. II shows the tensile strength of the unsulfonated styrene-isobutylene copolymer compared to the same Product, which contains 16.15 mol% SOjH and has different ion contents.

Curve A shows the tensile strength of the unsulfonated polymer as a function of the temperature. At 20 ° C the polymer has a tensile strength of 2640 kPascals. At 6O ⁰ C the tensile strength is 0. In contrast, has the polymer comprising about 16.15 mole% of SO ₃ H contains (curve B), at 2O ⁰ C a tensile strength greater than 4200 kPascals, and at 100 ⁰ C a tensile strength of almost 3500 kPascals.

By conversion to the Calciumionomere with only about 4 mol% SO3H (curve C) the product is obtained at 2O ⁰ C a tensile strength of greater than 6300 Pascals at 100 ⁰ C has a tensile strength of about 3750 Pascals.

The advantages of using a monovalent ion to form the ionomer are illustrated by curve D. At a conversion of about 12 mole% of SO 3 H groups in the sodium salt of the polymer at 20 ⁰ C has a tensile strength of from about 10500 Pascals, while the tensile strength at 100 ⁰ C is less than 2800 kPascals. Despite a high tensile strength at room temperature, the polymer can thus be easily processed at moderate temperatures.

It is apparent from the above examples that the polymer about 0.5 to 20 MOI ⁰ Zo SO; may contain H groups. Even with 1 mol% (SCb) ₁₁ M, where η is the valence of the metal ion M, an ionomer with improved properties is obtained. The ion content, ie the content of (SCb) _n M groups, is preferably about 2 to 18 mol%, a content of about 4 to 12 mol% being particularly preferred.

Example 71

In the preceding examples, the sulfonation of a purified homogeneous styrene-isobutylene copolymer has been described. It is not necessary to purify the product prior to sulfonation as described in this example. The material obtained according to Example 1 was prepared again with the difference that the catalyst was not destroyed by introducing the reaction mixture into isopropyl alcohol. Instead, the reaction medium (methylene chloride / hexane = 60:40) was kept at -40 ⁰ C and the styrene-isobutylene copolymers directly sulfonated with sulfur trioxide and triethyl phosphate. The polymer was isolated and analyzed. The product contained 5.57 mole percent sulfonated styrene. The material had the same properties in all respects as a carefully purified product (in dichloroethane).

It can easily be seen that the ionic polymer is a homogeneous styrene-isobutylene copolymer is superior thermoplastic material that can be processed by extrusion, injection molding, or pressing leaves. The product is used due to its unusual behavior towards solvents in the manufacture of rubber paints, alcoholic thickeners, flocculants, agents for Improvement of colorability and adhesives for bonding metals.

Example 12

A styrene-butyl graft polymer was prepared by the method of U.S. Patent No. 568 001 as follows: 100 g chlorobutyl HT-1066 were dissolved in a solvent mixture of 900 ml of heptane and 1000 ml of propane dissolved at -50 ⁰ C. 206.3 g of freshly distilled styrene and then 2.87 g of AIEt ₂ CI were added as a catalyst to the solution. The reaction takes 90 minutes. After this time the product was isolated and dried. The yield was 249.0 g. The product was extracted with acetone to remove the styrene homopolymer. The remainder of the material was made soluble in methyl ethyl ketone to separate the gelatinous precipitate. The fraction soluble in methyl ethyl ketone was isolated and dried.

5 g of this material were dissolved in 190 ml of dichloroethane. Then, following the procedure of U.S. Patent 3,072,618 sulfonated. 0.38 ml of triethyl phosphate and then 0.28 ml of sulfur trioxide were added at 5 ° C. After a reaction time of 10 minutes, the reaction was stopped by adding to isopropyl alcohol ended and the product isolated.

3S Analysis of the styrene-butyl graft copolymer gave an intrinsic viscosity of 0.77 in toluene and one styrene content determined by infrared analysis of 42%. A pressed board had a tensile strength of 19700 kPascals and an elongation at break of 375%.

The acid-base titration of the ionic styrene-butyl graft copolymer in a 1: 1 mixture of toluene and methanol with 0.1 H-KOC (CHj) ₃ showed that this product was 8.83 10 " ⁴ acid equivalents / g A sulfur content of 2.84% by weight was found.

The sulfonated styrene-butyl graft copolymer was converted into the ionic product by adding

was dissolved 1 mixture of toluene and methanol and 8.83 x 10 ~ ⁴ equivalents of sodium methoxide were added: in a first The precipitated product was dried and pressed at 149 ° C. under a pressure of 12 kbar for 10 minutes. The compact was thermoplastic and could be molded again under the above conditions. The pressed plate had a tensile strength of 9630 kPascals and an elongation at break of 225%. The ionic graft copolymer was decidedly stiffer than the nonionic graft copolymer.

The ionic graft copolymer exhibited one as compared with the nonionic graft copolymer

unusual solvent resistance. The Influences of Different Solvents! are in Table III compiled. The data show that the nonionic graft copolymer in certain organic Solvents have been greatly swollen or dissolved while the ionic graft copolymer is insoluble therein or was merely swollen.

Table III

Behavior of graft copolymers and ionic graft copolymers towards solvents

eres ionic graft copolymer

swells slightly

soluble

insoluble (not swollen)

insoluble

insoluble

insoluble

insoluble

solvent Graft Mix Polyr benzene soluble ⁶⁰ carbon tetrachloride soluble Heptane badly swollen Methanol insoluble 65 acetone insoluble Methyl ethyl ketone soluble water insoluble

Example 13

A styrene-chlorobutyl graft copolymer containing 63% styrene was prepared. 90.9 g of freshly distilled styrene were added to 24 g of chlorobutyl rubber HT-1066 in 313 ml of ethyl chloride plus 313 ml of methylcyclohexane. 0.14 g of AlEt ₂ Cl was used as a catalyst. The temperature was 14 ° C., the reaction time 172 minutes and the yield 107 g. The product was extracted with acetone. The methyl ethyl ketone fraction was separated off and analyzed. The intrinsic viscosity of this material in toluene was 0.36.

The sulfonation of the material was carried out in the manner described in US Pat. No. 3,072,618. 5.0 g of product were dissolved in 190 ml of dichloroethane, to which 0.57 ml of triethyl phosphate and 0.42 ml of sulfur trioxide were added at 5 ° C. When the reaction was complete, the product was isolated and analyzed. Acid-base titration showed the material to ^{contain 3.77 x 10 "3} equivalents of styrene sulfonic acid / g. The material was made ionic as follows: The product was dissolved in a 1: 1 mixture of toluene and methanol. Dissolve 3.77 x 10 " ³ equivalents of sodium methoxide were added. The solvents were evaporated and the dried ionic graft copolymer was isolated. This product could be ^{easily pressed at 149 °} C. and a pressure of 12 kbar over a period of 5 minutes. The material was very easy to reprocess under these pressing conditions. As in Example 12, this ionic graft copolymer was decidedly stiffer than the nonionic graft copolymer. The tensile properties of the two products are compared below.

Table IV

Material tensile strength kPascal elongation at break,%

Styrene-butyl graft copolymer 10 850 200

Ionic styrene-butyl graft copolymer 28100 2

Example 14

A commercially available styrene-butadiene rubber which contained 23% by weight of styrene and 77% by weight of butadiene and had a molecular weight (number average) determined by membrane osmometry of 120,000 was sulfonated as follows: The styrene-butadiene rubber was purified by dissolving 50 g of the rubber in 500 ml of hexane and precipitating the polymer in 10 1 methanol. The rubber was dried on a roller mixer at about 116 ° C. Polymers with various degrees of sulfonation were prepared by sulfonating 5 g samples of the purified material using an (EtO) ₃ PO: (SO ₃ ) _{3 complex.} The sulfonation was carried out in mixed solvents of cyclohexane and methylene chloride. The polymer was dissolved in the solvent mixture, whereupon the complexes prepared in methylene chloride were added dropwise with stirring. The reaction was carried out at 25 ° C for 10 minutes.

The conversion of the sulfonic acid containing polymers to ionomers was carried out by using the sulfonic acid polymer was reacted with a 2/1 excess of a NaOH solution in methanol. The polymers were isolated by adding the polymer solution to boiling water, thereby removing the solvents were evaporated and the polymer was precipitated. The isolated polymer was dried at 130.degree.

The various test results are summarized in Table V. It can be seen that the sulfonic acid polymer is soluble at 6.5 mol% SO3H, a sign that no crosslinking has taken place. The polymers were thermoplastic and could be pressed at 130 ⁰ C and 63,300 Pascals and umgepreßt.

Although sulfonation has been described as the sulfonation of the aromatic ring, it is believed that in polymers such as SBR, which are highly non-aromatic unsaturation, the sites of unsaturation are also sulfonated. It is not intended to be bound by any theory, but it is believed that the sulfonic acid components depending on the molar ratio of unsaturation to the aromatic ring and the reactivity of the sulfonated sites on the non-aromatic unsaturation Make and the aromatic rings are distributed. It is believed that the unsaturation are more reactive than the aromatic ring. In a polymer such as SBR, therefore, will be the predominant number of the sulfonic acid groups attached to non-aromatic unsaturation points.

55 Table V

Production and properties of a sulfonated styrene-butadiene copolymer (SBR)

SBR-Mcnge: Used 5 g NaOH + 40 ml CH ₂ Cl ₂ I SO ₃ H SO ₃ Na State of Solvent: (EtO) 3PO amount, Reaction Mole 100 ml of cyclohexane G CH ₃ OF Mol% Mol% product 1.37 x ΙΟ " ⁴ 0.0823 moles 0 0.48 0 soluble Available responsiveness in solution: 1.37 x ΙΟ " ⁴ CH ₂ Cl ₂ 0.0328 ml 0 0.50 soluble Used 0 SCb amount, mole Nfol 1.0 1.0 4.1 X ΙΟ " ⁴ 1.0 4.1 X ΙΟ " ⁴

Used
(EtO) ₃ PO amount,
Mole 19th 15 237 NaOH
G 40 ml CH ₂ Cl ₂ SO ₃ H
MoI- ⁰ /. SO ₃ Na
Mol% State of
Reaction
product Ii?
■ «·!
lit
i continuation 4.1 X 10 " 0 CH ₃ OH
ml 1.42 0 soluble 4.1 X ΙΟ "" 5g
100 ml of cyclohexane +
0.0823 moles 0.0984 0 0 1.51 soluble M. 8.2 X 10 " CH ₂ Cl ₂
Mole 0 1.0 2.82 0 soluble S. SBR amount:
Solvent:
Available responsiveness in solution: 8.2 X 10 " 1.0 0.1968 0 0 2.90 soluble I. Used
SCb amount, mole 1.92 x ΙΟ " ³ 1.0 0 2.0 6.5 0 - 1 1.23 X ΙΟ " ³ 2.0 0 I. 1.23 X ΙΟ " ³ 2.0 I. 2.46 X ΙΟ " ³ 3.0 1 2.46 X ΙΟ " ³ 5.76 X ΙΟ " ³

Mol%
SO ₃ H Mol%
SO ₃ Na tensile strenght
kPascal Module (50%)
kPascal Module (300%)
kPascal strain
% Deformation
rest at break,
% 0 0 245 2.73 2.9 570 400 0.48 0 525 2.8 4.41 680 350 0 0.5 448 2.8 3.71 800 350 1.42 0 1050 4.2 6.65 700 200 0 1.51 1610 6.3 11.9 630 40 2.82 0 3220 5.67 16.1 580 30th 0
6.5 2.90
0 3710
4550 10.9
11.9 26.4
42 650
340 5
0

The improvement in the physical properties can be clearly seen by comparing styrene-butadiene rubber with the same polymer that is both sulfonated and converted into the sodium ionomer is converted. The physical properties are summarized in Table VI.

Table VI

Properties of sulfonated styrene-butadiene rubber

These results clearly show that sulfonation improves the properties of the polymer. For example, just 0.48 mol% SO ₃ H in the polymer increases the tensile strength by more than 100%. The sulfonated polymers can be crosslinked in any conventional manner.

example

According to the method of US-PS 3265765 a styrene-butadiene block polymer was prepared which

Contained 30% by weight of styrene (S) and 70% by weight of butadiene (B). The polymer had the structure S-B-S. Here S the styrene units having a number average molecular weight of about 15,000; and B the butadiene units having a number average molecular weight of about 50,000. The polymer was based on that in Example sulfonated manner described. The results are shown in Table VII.

Table VII Used (EtO ^ PO amount,
Mole 10 g
0.158 moles SO ₃ H
Mol% M.
1 1.59 x ΙΟ " ³ ClCH ₂ CH ₂ Cl
ml 0.45 6.34 X ΙΟ " ³ 2.0 0.81 W. Sulphonation of a styrene-butadiene-styrene block copolymer 1.27 x ΙΟ " ² 5.0 1.24 I. Amount of polymer
Available responsiveness in solution
Solvent mixture 100 ml cyclohexane + 40 ml CH ₂ Cl ₂ 10.0 Amount of SO _{3 used}
Mole 1.59 x ΙΟ " ³ 6.34 X ΙΟ " ³ 1.27 x ΙΟ " ²

14th

Amount of polymer 10 g Complex formation Mole Ml % Sulfur Mol% SO ₃ H Amount of solvent (carbon tetrachloride) 200 ml Moles SO ₃ Complexing agents solvent in the product Styrene content des Polymers in Mol% 0.0144 p-dioxane 10 CH ₂ Cl ₂ 2.84 5.28 (Molecular weight, 0.0144 Numerical mean) 0.0144 (Et) ₃ N 15 CH ₂ Cl ₂ 0.29 0.54 18.8 0.0144 (175 000) 0.0313 THF 20 CH ₂ Cl ₂ 0.26 0.66 18.8 0.0313 (175 000) 0.0313 (Et) ₃ N 20 CH ₂ Cl ₂ 0.15 0.38 50.0 0.0313 (110 000) 50.0 (110 000)

Example 16

The styrene-isobutylene copolymers prepared according to Example 1 were sulfonated, but none of them were phosphorus-halous Lewis bases but other complexing agents were used. In Table VIII are the results sulfonation using p-dioxane, triethylamine and tetrahydrofuran as complexing agents compiled. The results clearly show that these Lewis bases are effective complexing agents.

Table VIII

Sulphonation of styrene-isobutylene copolymers

All products were soluble in the reaction medium. They had improved physical properties even without forming the ionomer. For example, the sulfonated polymer containing 1.24 mole percent SO ₃ H was more resistant to flow in a cold press. The improved physical properties were attributed to hydrogen formation. The product is easily converted to the ionomer in the manner described in Example 14. _%

It should be noted that styrene sulfonate ionomers are made from any aromatic-containing polymer can be. For example, polystyrene can itself be converted into an ionic polymer by the method according to of the invention. Surprisingly, by reacting polystyrene sulfonic acid formed a unique thermally stable product with an aromatic curing agent. The sulfonated Polystyrene must be sulfonated sufficiently to be soluble in polar solvents. Preferably should at least 85%, in particular 100% of the styrene units of the polymer are sulfonated.

Suitable polar solvents are, for example, water, Ci-Co-alkyl alcohols and Ci-Ce sulfates. Examples such solvents are methanol, ethanol, methyl sulfate, dimethyl sulfate and trimethyl phosphate. The solvent used must be polar (i.e. the dipole moment must be greater than 10 Debye). It must be non-aromatic and dissolve the aromatic curing agent.

Suitable curing or crosslinking agents are Ce-Cs aromatics, e.g. B. benzene, toluene or xylene, C ₂ -C ₂₅ -alkylbenzene, biphenyl, Ci-Qi-substituted biphenyl, triphenyl, Ci-Cn-substituted triphenyl, naphthalene, anthracene and phenanthrene. In short, any aromatic compound can be used provided that the aromatic ring or rings are not completely substituted.

To activate the curing or crosslinking, a catalyst is required, which is preferably in a Amount of about 0.1 to 10 wt .-%, based on polystyrene, is used. Catalysts of the general type are suitable Forniei

Al (R) _n X _n , or Sn (R) "X"

Herein, R is a C | -C ₈ -alkyl radical, X is a halogen atom, m and are integers from 0 to 3, where m + η = 3, and q and ρ are integers from 0 to 4, where q + ρ = 4, where ρ is either 2 or 4 in the case of q = 0.

Examples of such compounds are AlCl ₃ aluminum triethyl, aluminum diethyl chloride, aluminum ethyl dichloride, tin (II) chloride, tin (IV) chloride, vanadium pentachloride, zinc dichloride, boron trichloride, phosphorus trichloride, phosphorus pentachloride and phosphorus pentoxide. Friedel-Crafts catalysts are suitable as catalysts. Also suitable as catalysts are, for example, sulfuric acid, thionyl chloride, chlorosulfonic acid and oleum.

Example 17

A sulfonated polystyrene was prepared according to the method of US Pat. No. 3,072,618. About 5 g of polystyrene that had a number average molecular weight of 110,000, were dissolved in about 190 ml of dichloroethane. These The solution was then added to about 200 ml of dichloroethane at 0 ° C., which contained 5.0 ml of freshly distilled sulfur trioxide

and contained 3.7 ml of triethyl phosphate. After a reaction time of about 10 minutes, the product, in which about 90.6% of the styrene units were sulfonated, was washed and dried. The limiting viscosity was 1,942, as measured on a 0.5% solution in ethanol at 25 ⁰ C.

S example 18

The product prepared according to Example 17 was using sulfuric acid as a catalyst and Biphenyl vulcanized as a vulcanizing agent in the following amounts.

ίο Table IX

Vulcanization mixtures

Mix no.

Parts by weight
Sulfonated polystyrene

Biphenyl

20 3

4th
5

0 25 42 67 84

The product was isolated by removing the catalyst and evaporating the solvent. the thermal stability of these products is given in Table X. Mix numbers in Table X correspond to the numbers of the mixture in Table IX.

Table X

Thermal stability of vulcanized products
(Nitrogen atmosphere, heating rate 6 ° C / minute)

mixture
Temp., ⁰ C

25th 50 100 100 100 100 100 100 100 100 100 100 100 40 200 99 100 100 100 100 300 98 100 100 100 100 400 93 100 100 100 100 500 85 100 98 98 99 45 600 73 93 97 90 94 700 67 89 90 84 89 800 62 84 86 81 83 900 61 81 85 78 79

These values show that the self-vulcanized material (Mixture 1) is not as stable as a material that contains an additional vulcanizing agent (e.g. biphenyl). The product obtained has excellent Heat resistance and is suitable as a lining for reactors operating at high temperatures and generally for all purposes where high thermal stability is important.

Claims (7)

Patent claims: 1. sulfonated polymers containing aromatic rings based on styrene-butyl rubber graft copolymers, homogeneous styrene-isobutylene copolymers, styrene-butadiene copolymers or styrene-acrylonitrile copolymers, in which the sulfonic acid group is neutralized, characterized that the copolymer is sulfonated with 0.08 to 20 mol% of sulfonic acid groups, based on the copolymer, wherein about 1 to 100% of the sulfonic acid groups with a compound from the group of the primary, secondary or tertiary amines and the metal salts with a metal from one of the groups II, III, IV, V, VIb, VIIb and VIII of the Periodic Table or a mixture of these metals to form the corresponding Amine or metal salts are neutralized. 2. Process for the preparation of sulfonated polymers according to claim 1 by dissolving the to be suJibnenden Copolymers in a suitable solvent and reacting with a SOj complex, the by reacting a Lewis base containing nitrogen, phosphorus or oxygen with a sulfur trioxide donor has been prepared as a sulfonating agent, characterized in that a polymer with a degree of sulfonation of 0.08 to 20 mol%, based on the polymer, and that one then the sulfonieite polymer with a compound from the group of primary, secondary or tertiary amines and the metal salts in which the metal component is a metal from group II, III, IV, V, VIb, VIIb and VIII of the Periodic Table or a mixture of these metals is converted and so formed polymers isolated. 3. The method according to claim 2, characterized in that nitrogen-containing Lewis bases of the general formula (1) R ₂ -N or (2) ₂ - are used, in which R], R2 and R3 are independently hydrogen, Ci-C36-alkyl, -aryl, -alkaryl and -aralkyl and their substituted analogues, but at least one radical R is not hydrogen, R4 is C3-C36 -Alkylene radicals and their substituted analogs and R5 represents hydrogen, Ci-C ₃ 6-alkyl, -aryl, -alkaryl or -aralkyl. 4. The method according to claim 2, characterized in that a nitrogen-containing Lewis base of the general formula R ₄ / is used in which Ri, R2, R3, R4 and R5 independently of one another for halogen atoms, hydrogen atoms, Ci-C36-alkyl radicals, -aryl, -alkaryl, -aralkyl or substituted analogues of these radicals. S. The method according to claim 2, characterized in that oxygen-containing Lewis bases of the general formula ^R > R (1) O (2) rT ^ Ö or O O R ^{y Xr} / ^Rl are used in which Ri and R _{2 are} independently C ₂ -C36-alkyl, -aryl, -alkenyl, -aralkyl or their substituted analogues and R3 is a C3-C36-alkylene radical or a corresponding substituted C3-C36-alkylene radical . 6. The method according to claim 2, characterized in that the Lewis bases are esters of the general formula O
R ₁ -COR ₂ in which Ri and R2 are independently Q-Cio-alkyl radicals, phenyl radicals or benzyl radicals, are used. 7. The method according to claim 2, characterized in that the Lewis base is organic phosphorus compounds the general formula R ₁ R. A A (1) R ₂ -BP (O) or (2) R ₂ -BP C C