DE1099741B - Process for the preparation of anion exchange resins with primary or tertiary aminoalkyl groups - Google Patents

Description

Process for the preparation of anion exchange resins with primary or tertiary amino alkyl groups with secondary or tertiary anion exchange resins Aminoalkyl or quaternary ammonium alkyl groups are known and can, for example by reaction between an insoluble, crosslinked polymer, the halogen alkyl groups, z. B. chloromethyl groups, and a primary, secondary or tertiary Amine can be produced. The corresponding reaction with ammonia, from which one expected introduction of primary amino groups, but mostly resulted in secondary ones or tertiary amino groups, and to the best of our knowledge, anion exchange resins are the Contain nitrogen entirely or predominantly as primary aminoalkyl groups, unknown.

According to this invention we leave an insoluble, crosslinked polymer, containing haloalkyl groups with hexamethylenetetramine to form an addition compound react and decompose these to convert the hexamethylenetetramine groups into primary or transfer tertiary amino groups. The resulting connections are Ion exchange resins in which the ion exchange groups are exclusively or in are predominantly primary or tertiary aminoalkyl groups.

The addition reaction can be expressed by the following equation become: R-A-X + N4 (CH2) 6 t R - A - Ni + (CH2) 6X where X is a halogen atom, A is an alkylene group Q, H2 (n = integer) and R-A-X represents a halogen-alkylated polymer. That Addition product thus contains quaternary ammonium groups and itself has anion exchange properties.

The addition product is decomposed by hydrolysis with acid or Alkali to a resin of the formula R - A - NH2 with primary aminoalkyl groups by adding one z. B. with concentrated aqueous hydrochloric acid or alcoholic hydrogen chloride cooks. Alternatively, the addition product can be allowed to react with sulfur dioxide, to form an alkylaminomethyl sulfate: R-A-NH-CH2-O-SO2H which then by acid hydrolysis in addition, the corresponding primary amine is decomposed.

Shall the addition product in a resin with tertiary aminoalkyl groups are transferred, it is treated with 25 to 1000/0 formic acid.

The process of the invention is very general in the case of haloalkylated, crosslinked polymers applicable.

A useful class of base polymers is made by copolymerization a compound having a polymerizable double bond with a crosslinking agent obtained from two or more polymerizable double bonds. Every component can be aromatic or aliphatic, the haloalkylated groups can either in one of the original Monomers be present or after formation of the polymer be introduced into this. Suitable monomers with a polymerizable double bond are z. B. styrene, vinyl toluene, vinyl naphthalene and acenaphthylene; as a crosslinking agent divinylbenzene, ethylene dimethacrylate, divinylketone, etc. are suitable

Another class of polymers are haloalkylated phenol-formaldehyde resins.

The haloalkyl group is preferably chloromethyl, which is suitable Way by treating the polymer with chloromethyl ether and a Friedel-Crafts catalyst or introduced into the same with methylal and anhydrous aluminum chloride can. Other suitable haloalkyl groups are bromomethyl and chloroethyl.

A polymer which already contains haloalkyl groups that are im Were introduced during the course of the polymerization, for example polyvinylchloromethyl ether, which is caused by the reaction of polyvinyl alcohol, formaldehyde and hydrogen chloride can be won.

The reaction of haloalkylated polymer with hexamethylenetetramine can be carried out by refluxing the polymer with a hexamethylenetetramine solution in a solvent, preferably one that contains the haloalkylated polymer causes it to swell, is heated. The solvent itself must of course not react with the haloalkylated polymer. Suitable solvents are, for example Ethylene dichloride, chloroform and carbon disulfide. It was found that Chloroform is a particularly satisfactory solvent, when chloromethylated, crosslinked polystyrene as haloalkylated polymer is used.

The mixture is heated until a complete reaction has taken place Has. The time required for this is generally 1 to 12 hours, depending according to the solvent used and the type of polymer.

Example 1 The example illustrates the manufacture of a primary Aminoalkyl resin from hexamethylenetetramine addition product. It became a grainy, by suspension polymerization of a mixture of 45 g of styrene and 5 g of commercially available Divinylbenzene (5001, ig) and 0.1 g of benzoyl peroxide produced polymer is chloromethylated, after chloromethylation by boiling for hours on a reflux condenser with 40 g in 400 ml of hexamethylenetetramine dissolved in chloroform in a hexamethylenetetramine addition resin transferred, the product filtered off and washed with water.

In order to convert this resin into a primary aminoalkyl resin, boiled it with 200 ml of concentrated hydrochloric acid for 20 minutes. After removing the excess Acid and water wash was the anion exchange capacity of the product 3.4 mvalig dry resin.

Example 2 Example for the preparation of a tertiary aminoalkyl resin: A polymer was produced in spherical form as in Example 1, except that all of the positions of styrene acenaphthylene was used. This product has been chloromethylated and converted into the hexamethylenetetramine addition resin. The product was filtered off, with water washed out and mixed with 200ml 9001, iger formic acid. The mixture was then gradually refluxed with evolution of carbon dioxide. The refluxing was continued for 1 hour.

After separating off the excess formic acid and after Washed out with water, the finished resin had an anion exchange capacity of 3.1 mvallg dry resin.

PATENT CLAIM 1. Process for the preparation of anion exchange resins with primary or tertiary aminoalkyl groups, characterized in that one Addition compound consisting of hexamethylenetetramine and an insoluble, crosslinked Polymer which has haloalkyl groups is available for converting the Hexamethylenetetramine groups into primary or tertiary amine groups with acid or Alkali is decomposed.

Claims (1)

2. The method according to claim 1, characterized in that the hexamethylenetetramine groups be converted into primary amino groups by the addition compound a is subjected to acidic or alkaline hydrolysis. 3. The method according to claim 1, characterized in that the hexamethylenetetramine groups by treating the addition compound with formic acid into tertiary amino groups be transferred. Considered publications: German Patent Specifications No. 829223, 841 796, 848 256, 848257.