DE2162951A1 - METHOD OF PRESENTATION OF ADSORBENTS - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN-Bayerverk f £ Jjg_ jQ-jf Central area

Patents, Maiken and Licenses

Se / HG

Process for the preparation of adsorbents

. ——:;

In the context of extraction chromatography, the selective Separation of elements used as stationary phase adsorbents, which consists of an inert carrier material and a compound » capable of interacting with ions or molecules is, - the so-called extraction agent, consist " Known carrier materials are, for example, aluminum oxide, kieselguhr, cellulose or compounds such as polyethylene, Polypropylene and polytetrafluoroethylene. It is also known that macroporous copolymers of styrene and bivinylr to use benzene as a carrier material. The corresponding Extractant is made by soaking on the various Carrier materials applied and remains there as a result of Sorption capacity of the carrier material or penetrates into shape a swelling process in the carrier materials »

Adsorbents produced in this way have a number of disadvantages len. Is sorption the key factor in staying of the extractant on the carrier material, these carrier materials must be in fine powder form to have a sufficiently large surface. This means that they can only be used to a limited extent for filling columns,

9625/0977

as they cause high flow resistances due to their fine powdery form. Carrier materials to which the extractant was conveyed with the help of a swelling process, show poor kinetics, i.e. the exchange between the mobile and stationary phase is too slow. The elution curves show tail formation. All of these adsorbents are in common that they release the extractant to the mobile phase in a relatively short time and thus only a small time Own lifetime.

It has now been shown that adsorbents based on synthetic resins are obtained which do not have the disadvantages mentioned above if the procedure is such that an extractant, an extractant mixture or the solution of an extractant is added to a mixture of monovinyl and polyvinyl compounds to be polymerized added in a solubilizer, wherein the extractant, the extractant mixture or the solution of the extractant in a solubilizer is a solvent for the monomers, but not for the polymer. All vinyl aromatic compounds such as, for example, styrene, methylstyrene, acrylic acid, methacrylic acid, acrylonitrile, acrylic acid esters, methacrylic acid esters, vinyl anisole or vinyl naphthalene can be used for the production of the adsorbents according to the invention , Divinyixylene, Divinylnaphtalin, Divinyläthylbenzöl in question. The amount of the FoIyvinylverbindungen used can vary within wide limits? In general, the content of such compounds will be between 5 % and 70 % .

Suitable extractants are all those compounds which are used as extractants in extraction chromatography are known. Examples are: tributyl phosphate, Triocty! Phosphate, tri-n-octylamine, tributylamine, Dodecylamine, 9-amino-heptadecane, bis- (2-ethyl-hexyl) -phosphate,

Le A 14 052

2-mefchyl-pentanone, also carboxylic acids, such as Caproic acid or pelargonic acid. An overview of such Compounds that are used as extraction agents or extraction agent devices in the context of extraction chromatography can be found in "Eurochemic Technical Report", ETR.271. (June 1971).

These are used as solubilizers for the extractants Compounds in question that are both solvents for the extractants and for the monomers. Such Compounds are, for example, hydrocarbons such as paraffin oil and white spirit or halogenated hydrocarbons such as chlorododecane.

To prepare the adsorbents, the monomers in the Extractants a mixture of the extractants or the solution of an extractant in a solubilizer are dissolved and then polymerized. Such solutions are used to produce bead-shaped adsorbents of the monomers in the aqueous medium using stabilizers such as methyl cellulose, hydroxyethyl cellulose suspended and then polymerized. Peroxides such as, for example, are primarily used as catalysts Benzoyl peroxide, lauryl peroxide or compounds such as azo-bis-isobutyric acid nitrile,

The inventive method describes the representation of Adsorbents with a high content of extractants. The delivery of the extraction agent to the medium to be processed is practical in the case of the adsorbents produced according to the invention completely suppressed. The elution curves of the adsorbents according to the invention show practically no tail formation. To the Comparison are shown according to the invention in Figure 1 and 2 elution curves produced adsorbents with the elution curves

14 05 ".

such adsorbents which were obtained in a manner known per se by impregnating the carrier materials. This curve was obtained by eluting adsorbents loaded with uranyl nitrate with water Diviny benzene!. As extractant tributyl was used .. the curves in Figure 1 differ from Figure 2 by the content of the studied adsorbents of divinylbenzene. So in Figure 2 adsorbents are compared with a content of 25% divinylbenzene. the curves labeled I Both figures are the elution curves of the adsorbents produced according to the invention. These curves clearly show that the tail formation, which can be clearly seen in the case of the adsorbents produced in a manner known per se, is practically suppressed in the case of the adsorbents produced according to the invention he one knows a significant increase in capacity of the adsorbents according to the invention.

Le A 14 052 - 4 -

309825/0977

Example 1:

A solution of 13.4 parts of 60.8% divinylbenzene, 136.6 parts of styrene, 1.5 parts of benzoyl peroxide and 350 parts of tri- n-butyl-phosphate, where * the mixture is heated with stirring in the course of 3 hours at 80 ⁰ C., kept for 10 hours at this temperature and then heated for 1 hour at 9O ⁰ C * After cooling, is separated from the aqueous phase and the bead polymer obtained was briefly washed with water.

Example 2 ;

The procedure was as in Example 1, only with the difference that a solution of. 32.9 parts of 60.8% strength Divinylbenzene, 167.1 parts of vinyl toluene, 2 parts of benzoyl peroxide and 300 parts of tri-n-buty! Phosphate was added.

Example 3 t

The same procedure as in Example 1 was followed, with the difference that that 49.3 parts of 60.8% strength divinylbenzene, 150.7 parts of styrene, 3 parts of azo-bis-isobutyronitrile and 300 parts of dodecylamine were given. '

Example 4 ;

The same procedure as in Example 1 was followed, with the difference that that for the initial charge 65.7 parts of 60.8% divinylbenzene, ' 134.3 parts of styrene, 2 parts of azo-bis-isobutyric acid nitrile and 150 parts of chlorododecane and 150 parts of phosphoric acid-bis- (2-ethyl-hexyl-ester) was given.

Le A 14 052 - 5 -

30982S / 0977

Example 5 :

The procedure was as in Example 1, only with the difference that to the initial charge 65.7 parts of 60.8% divinylbenzene, 134.3 parts of styrene, 3 parts of azo-bis-isobu'fctersäurenitril, 240 parts of 1-chloro-dodecane and 60 parts of bis- (2-ethyl-hexyl) -amine were given.

Example 6 ; ,

The procedure was as in Example 1, with the difference that 32.8 parts of 60.8% divinylbenzene, 67.2 parts of styrene, 1 part of azo-bis-isobutyric acid nitrile and 150 parts of tricaprylamine were added.

example 1 :

The procedure was as in Example 1, only with the difference. that for the template 142.6 parts of 56.1 ^ divinylbenzene, 57.4 parts of styrene, 6 parts of azo-ms-isobutyric acid nitrile and 300 parts of 9-amino-heptadecane were given,

Example 8 ;

'' The procedure was as in Example 1, only with the difference that for the template 178.3 parts of 60.8% divinylbenzene, 21.7 parts of styrene, 6 parts of azo-bis-isobutyronitrile and 300 parts of bis (2-ethyl-hexyl) amine were added.

Example 9 '.

The procedure was as in Example 1, but with the difference that "to the template 164.4 parts of 60.8% divinyl benzene, ι 35.6 parts of styrene, 6 parts of azo-bis-isobutyronitrile and

Le A 14 052. - -. . .--- 6. ^ "
- "3 nights 9 8 2 5/0 9 7.7

216295Τ

300 parts of 2-ethylhexylamine were added, Example 10 :

The procedure was as in Example 1, only with the difference, ι that for the template 123.9 parts of 60.5? 6-strength divinylbenzene, *

26.1 parts of styrene, 1.5 parts of benzoyl peroxide and 350 parts Tributyl phosphate were given.

Example 11 :

To a template of 307 parts of water and 27 parts of a 2.5% strength * methyl cellulose solution is a solution of 21.7 parts of 96.8 ° / o ~ divinyl benzene, 8.3 parts of styrene, 0.3 parts of benzoyl peroxide and 70 Parts of tri-n-butyl phosphate given. While stirring, the mixture is ^{heated to 80 °} C. over the course of 3 hours, left at this temperature for 15 hours and then heated ^{to 90 ° C. for 1 hour.} After cooling, the aqueous phase is separated and the bead polymer obtained is briefly washed with water.

Example 12 :

A solution of 124.4 parts of 95.5% divinylbenzene, 75.6 parts of styrene, 2 parts of benzoyl peroxide and 150 parts of caprylic acid is added to an initial charge of 1000 parts of water and 87 parts of a 2.5 % methyl cellulose solution 150 parts of phosphoric acid tris (2-ethyl-hexyl) ester are added. ^{The mixture is heated to 80 °} C. over the course of 3 hours with stirring, left at this temperature for 10 hours and then heated ^{to 90 ° C. for 1 hour.} After cooling, it is separated from the aqueous phase and the bead polymer obtained is briefly washed with water.

BAD OBtGtNAL

Example 13 :

30 parts of 96.8% divine / benzene, 70 parts of tributyl phosphate and 0.7 part of benzoyl peroxide are added to an initial charge of 326.4 parts of water and 13.6 parts of a 2.5% strength methyl cellulose solution. The mixture is heated with stirring in the course of 3 hours at 80 ⁰ C, left for 10 hours at this temperature and so Dabb heated for 1 hour at 90 ⁰ C. After cooling, the bead polymer is washed U _n ^] i _{URZ w} ith water separated from the aqueous phase.

Example 14; ■ -_ ■ .. ■:. ;

The procedure was as in example 1, only with: the difference, that to the template 42.6 parts of 52.8% divinylbenzene, 407> 4 parts of styrene, 4.5 parts of azo-bis-isobutyric acid nitrile, 25 parts of methyl tricapryl ammonium chloride and 25 parts of chlorododecane were given. . "..-." .-

Example 15:. . - - ν. '

The procedure was as in Example 1, only with the difference that to the template. 127.1 parts of 52.8% divinylbenzene, 172.9 parts of styrene, 4 parts of azo-bis-isqbutyronitrile and. 100 parts of tributylamine were given.

Example 16:

The procedure was as in Example 1, with the difference that 33.5 parts of 96.8% divinylbenzene, 16.5 parts of styrene, 0.5 part of BP, 360 parts of 1,1,2,3,3-penta-, chloropropane and 90 parts of trioctyl phosphate were added.

^{Le A 14} ° ³² 3098 2 "$ / 09 7 7

Claims (4)

Claims ^ T. A process for the production of adsorbents based on * synthetic resins, characterized in that one to ^s polymerizing mixture of monovinyl and polyvinyl compounds an extractant, an extractant mixture or the solution of an extractant in a solubilizer adds, the extracting agent, the extraction agent. middle! mixture or the solution of the extractant in one Solubilizer a solvent -for the monomers, not however represents for the polymer. j 2. The method according to claim 1, characterized in that the extractant, the extractant mixture or the solution of an extractant in a solubilizer in amounts of at least 10 % is used based on the weight of the monomers, "^ 3. Adsorbent, characterized in that an extractant or an extractant mixture during the polymerization is incorporated into the crosslinked polymer structure. 4. Use of the adsorbents to separate metal ions. Le A .14 052. - 9 - ________— ._ ^ _{0 9 8 2} ^ / Q 9 ₇ Blank page