CS241859B1 - Polymeric material with bound alkyldithiocarbamate groups and process for its preparationPolymer material with bound alkyldithiocarbamate groups and process for its preparation - Google Patents

Abstract

The subject of the invention is a polymer material with bound alkyldithiocarbamate groups, characterized in that 0.1 to 90% of the theoretical amount of units of the general formula (I) Z---- N---- R i = 5 (I) I s “ is bound to the polyacrylate, polymethacrylate, polystyrene or polyaspartamide chain, where R is an alkyl or hydroxyalkyl with 1 to 3 carbon atoms and Z is a group connecting the alkyldithiocarbamate unit to the polymer chain, selected from the group comprising -cooch2ch(ch)ch2-, -ch2conhch2ch2-, -C0NHCH2CH2- and -^=^-0^0¾. . The alkyldithiocarbamate group is part of the side chain, not the main chain, which significantly improves its accessibility. This is also indicated by the high sorption capacity for metal ions, as documented in the examples. The generality of the synthesis thus allows obtaining polymers with alkyldithiocarbamate groups in soluble form, but also in cross-linked form as a gel or macroporous sorbent.

Description

The invention relates to a polymeric material having alkyldithiokarbamátovými groups and způsot / ⁴ of its preparation.

The alkyldithiocarbamate group (hereinafter ADTC group) is known for its chelating ability for heavy metal ions. Its chelating properties are well studied and have led to the use of this agent to mask, remove, determine and divide heavy metal ions. Mostly, sodium diethyldithiocarbamate or similar low molecular weight compounds derived from piperidines are used for this purpose. The resulting heavy metal chelates are generally highly lipophilic so that they can be shaken into water-immiscible solvents such as chloroform. The chloroform solution can be further subjected to chromatography to determine the metal ions separately in the mixture. Other methods utilize differences in equilibrium constants and thus displacement of individual metal ions. The starting reagent in this case is generally zinc diethyldithiocarbamate, dissolved in an organic solvent, in which the metal ions contained in the aqueous phase K * of the zinc contained in the organic phase are exchanged by shaking with the aqueous solution. Water-soluble alkali metal diethyldithiocarbamates have been proposed as an antidote in the treatment of heavy metal-containing preparations, for example cis-diamine-indichloroplatinum (II) complex.

For many applications, it is preferable to anchor the ADTC groups on a polymeric support. For example, D. S. Hackett and S. Siggia (in Environmental Analysis, G.W. Ewing, Academic Prhess, New York 1977 »p. 253) described a sorbent prepared by crosslinking polyethyleneimine and subsequently derivatizing the amino group of the main polymer chain with carbon disulfide. This sorbent has been used with success for the analysis of trace elements in urine (R. M. Barnes, J. S. Genna, Anal. Chem. 51>

- 2 241 859

1065, 1979), the determination of transition metals, rare earths and thorium (A. Miyazaki, RM Barnes, Anal. Chem. 53,299, 1981) ^{and the} like.

The disadvantage of said sorbent is its low chemical definability, difficulty in preparation, and finally the only available form. These disadvantages are overcome by the present invention, making it possible in a simple manner to prepare polymeric material and alkyldithiocarbamate groups in both soluble and crosslinked form.

The object of the invention is a polymeric material with attached alkyldithiocarbamate groups, characterized in that from 0.1 to 90% of the theoretical number of units of the general formula I - Z - N - R is bonded to the polyacrylate, polymethacrylate, polystyrene or polyaspartamide chain.

I 1 X

Wherein R is an alkyl or hydroxyalkyl of 1 to 3 carbon atoms and Z is a linking group of an alkyl dithiocarbamate unit to the polymer chain, selected from Be the group consisting of -COOCH2CH2CH3CH3CH3-, -CH2 CONHCH3CH3- , -COCH ₂ CH ₂ - and --CH ₂ CH ₂ .

The polymeric material with alkyldithiocarbamate groups can be prepared by the process according to the invention, characterized in that the starting polymeric material containing secondary amino groups of the general formula (Ii) in the side chain - Z-NH-R (Ii) wherein Z and R have the same meaning as above, is treated with up to five-fold molar excess of hydroxide or alkali metal ahličitanu the decisive ¹ 'released by the water and up to twice the molar excess of carbon disulfide, based on the contents of both groups (if any), and at a temperature of 10-50 ° C, reacted for about 24 hours.

In addition to the already mentioned advantage of ease of preparation and product handling, it should be noted that the alkyldithiocarbamate group is part of the side chain rather than the main chain, thereby significantly improving its accessibility. This is also indicated by the high sorption capacity for metal ions. The generality of synthe241 859 sy thus makes it possible to obtain the polymers also in a cross-linked form, whether as a gel or macroporous sorbent.

The invention is illustrated by the following examples:

Example 1.

A spherical macroporous carrier prepared by copolymerization of glycidyl methacrylate and ethylenedimethacrylate (1 part) was suspended in 1,4-dioxane (3 parts) and isopropylamine (5 parts) was added. After 24 hours of gentle shaking at elevated temperature, the support is filtered and washed with water until the reaction to amine disappears. The reaction product has -COOCH CH (OH) CH NHCH (CH) groups attached to the polymethacrylate chain. Then, resuspended tin was again in 3 parts of 2 rool of 1 sodium hydroxide (NaOH-ϊ) and 0.5 parts of carbon disulfide (CS4) was added and shaken vigorously for 24 hours at room temperature. Then the polymer was filtered off, washed with acetone, optionally extracted with acetone. Composition: C 47 · 6 $, H 6.17%, S 6.98%, N 2.51% · Shake with copper sulfate solution (CuSO 4) and determination of copper loss revealed a capacity of 1.12 romol / g.

Example 2

A spherical macroporous carrier as in Example 1 was reacted with 1 part of ethanolamine dissolved in 5 parts of water to obtain a polymer bearing the -COOCH ₂ CH (OH) CH ₂ NHCH ₂ CH ₂ OH groups. The further procedure was similar to Example 1. The observed capacity was 1.24 mirol / g.

Example 3

Polysuccinimide of an average mole weight of 20,000 was dissolved in a 10% solution in dimethylformamide. A 1.25 molar excess (per succinimide unit) of N- (2-hydroxyethyl) ethylenediamine was added and reacted at room temperature with stirring for 24 hours. Cleavage of the polysuccinimide with an amine gave a polyaspartamide chain, with side groups -CH ₂ COH (CH ₂ ) ₂ NHCH ₂ CH ₂ OH, which was dialyzed with water. Polymer solution adjusted by evaporation to original volume and added 5-fold molar amount of sodium carbonate (Na_CO) and 2-fold

241 859 carbon disulphide (CS_). Shaken for 24 hours under pH control, which must be kept above 9.5 · Purified by dialysis against 0.02% Na CO. Sulfur content

Λ J

19.51%, i.e. 87.5% of theory.

Example 4

The polysuccinimide, as in Example 3, was treated with a 0.2 molar excess of N- (2-hydroxyethyl) ethylenediamine for 48 hours and then for 6 hours with 2 equivalents of ethanolamine. Other procedure as in Example 3 The resulting polymer had 10.2 mol. % Of ADTC groups.

Example 5

A copolymer of N- (2-hydroxypropyl) methaceylamide and 4-nitrophenyl methacrylic ester was dissolved in dimethylformamide (DMF). To the solution was added 1.5 molar amount (per nitrophenyl esters) of N- (2-hydroxyethyl) ethylenediamine and allowed to react for 24 hours. The product contained a -C0NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ OH attached to the methacrylate chain. The polymer was precipitated with acetone: ether

1: 1a dissolved in 5% aqueous sodium carbonate (NagCO). A 4 molar excess of carbon disulfide (CSg) was added with shaking through the noe. The obtained polymer was purified by dialysis against 0.02% Na 2 CO. The yield corresponded to 84% substitution (based on nitrophenyl groups).

EXAMPLE 6 Part of Poly (N-Methylaminoethyl) styrene [beta] (2%) crosslinked 2% technical divinylbenzene containing attached groups on the backbone

1 H "CH" NHCH ", was suspended in a mixture of 5 parts

Λ J θ

0.2 mol / l KOH and 2 parts carbon disulfide and the mixture stirred at 5 ° C for 10 hours. Mymarbyl was filtered off, washed with several volumes of water and alcohol and dried. Elemental analysis revealed a 4.5 wt. open.

Claims (2)

OBJECT OF THE INVENTION 241 859 CLAIMS 1. A polymeric material with attached alkyldithiocarbamate groups, characterized in that from 0.1 to 90% of the eoretic amount of the units of the general formula I - Z-N-R is bonded to the polyacrylate, polymethacrylate, polystyrene or polyaspartamide chain. C = S (X) s wherein R is alkyl or hydroxyalkyl of 1-3 carbon atoms and Z is a group linking the polymer alkyldithiokarbamátovou unit SOLUTIONS hard, selected from the group -COOCH CHÍOEQCHg- ^ -CH ^ CONHCHgCHg-, -C0NHCH ₂ CH ₂ - and - <^ 2 ^ “ ^{CH2 CH2} · 2. A process according to claim 1, wherein the starting polymeric material containing the secondary amino groups of formula (a) in the side chain is: -Z-NH-R (li) where Z and R have the same meaning as in point 1, mixed with up to 5-fold molar excess of alkali metal hydroxide or carbonate dissolved in water and up to 2-fold molar excess of carbon disulfide, both based on the group (li) content , and allowed to react for up to 24 hours at 10 - 50 ° C.