DE2364368A1 - Crosslinked vinylaromatic copolymer with thiourea gps. - with high metal (e.g. mercury) cpds. absorption power - Google Patents

Abstract

The resins comprise a cross-linked macroporous vinylaromatic polymer is which >=10% aromatic rings are substituted by >=1 of the gps. (I)-(III) (where x, y and z are each 0-3, n is 0-2, R1 R2 and R3 are H, 1-6C opt. branched alkyl, 2-6C alkenyl, 5-6C cycloalkyl or an aryl or aralkyl opt. substd. by 1-3C alkyl, alkoxy or halogen). When x, y and z are not O (I) comprises 1-95% pref. 10-60%, (II) 90-40% pref. 85-10% and (III) 1-95% pref. 5-80%, and when z is O (I) compsns. 5-100 % and (II) 95-0%, based on (I)+(II)+(III). The resin are further characterised by a pore volume of 20-80%, pref. 30-60% and a surface of 10-500 m2/g pref. 20-200 m2/g. The resins are used for absorbing metal cpds. from solution esp. Hg and Ag salts and have high absorption power and speed even at pH zero. They are used in technical filters.

Description

Bayer Aktiengesellschaft 236436 β

Central area of patents, trademarks and licenses

509 Leverkusen, Bayerwerk Se / Cr

Resins for separating heavy metals

The invention "relates to new, crosslinked" macroporous, vinylaromatic © Plastics, the thiourea groups, contain processes for their production and their use for adsorption of metal ions, in particular of precious metal and mercury ions.

From DOS 2.312.253, uncrosslinked, vinyl aromatic polymers, for example 'polystyrene resins, are known which contain amino groups and thiourea groups of the formula -NHCSNHR as functional groups, where R is a hydrogen atom, ei * ¹ alkyl _r aryl - or acyl radical. Their use for removing heavy metal ions from solutions is also described in DOS 2.31.2.233. The absorption capacity of the synthetic resins described in DOS 2.312.233 is, however, less than satisfactory in the strongly acidic pH range, since undesirably large amounts of heavy metals, for example mercury, remain in the solutions. In addition, the production of these synthetic resins with good hydrodynamic properties, which are the prerequisites for technical use, is complicated and associated with considerable difficulties.

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The present invention relates to synthetic resins made from a crosslinked, macroporous vinylaromatic base polymer made from mono- and polyvinyl compounds, which have a pore volume of 20-80 vol 10-500 m2 / g, preferably 20-200 m2 / g, and at least 10 % of its aromatic nuclei through a maximum of 3 functional groups of the general formula

pL-IJR ₁ -C-NR R

II ρ - [(GH ₂ ) -KR h |

- ~

and or

III P ₁ [

per core ~ 'S

are substituted, where

P ₁ an aromatic core of the ..macroporous -Gmind-

polymers,. -.

- n. is an integer between 0 and 2, R ₁ , Rp and FU are identical or different and are independent of one another. Hydrogen atom, a straight-chain or branched C. -CV-alkyl, C2-Cg-alkenyl-, a Cc-Cg-cycloalkyl or an _{aryl or aryl optionally substituted by C 1} -C - ^ - AlKyI, alkoxy or halogen Mean aralkyl radical,

^ 2 one of p. different core of the macroporous Represents base polymer, and where in the case of .. ".

III = 0 and R ₂ = ■ hydrogen;

the proportion of I 5 - 100 %>

that of II 95-0 %
in the case of III = 0 and R ₂ = R ^ = _f hydrogen. ■.

the proportion of I 5- 100 %,

that of II 95- 0 % "

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. "and - in case III not equal to O ■ · ■ - the proportion of I 1 -? u %, preferably IC - 60

from II 98-4 %, preferably 83-10> £ and ■. from III 1 - ■ 95 "-9 ^, preferably 5 - QO%

■ based on the sum of the functional groups.

The following may be mentioned as C ₁ -Cg or C ₁ -C, alkyl radicals: methyl, ethyl, propyl, butyl, pentyl and hexyl, methyl, ethyl and propy being preferred

Examples which may be mentioned as C2-Cg-alkenyl radicals are: allyl, Propenyl and butenyl, allyl being preferred.

Cyclopentyl and cyclohexyl may be mentioned as C _{t --Cg cycloalkyl radicals.}

The following may be mentioned as optionally substituted aryl or aralkyl radicals: phenyl, benzyl, naphthyl, toloyl, "o-chlorophenyl, p-hydroxyphenyl, p-ethoxyphenyl and methoxyphenyl.

Preferred are those of the synthetic resins according to the invention which have a porosity of 30-60% by volume, an inner surface of 20-100 m / g. have and in which the proportion of the functional groups of the general formula I 5-100, preferably 10-90%, that of the general formula II 95-0, preferably 90-10 % based on the total amount of functional groups and in which η = 1 and R ,. = JL, = hydrogen and R-, stands for methyl, phenyl, allyl - or benzyl.

Preference is also given to those of the synthetic resins according to the invention which have a porosity of 30-60 vol .-? O, an inner surface area of 20-100 m / g and in which the proportion of the functional groups of the general formula I 5-100 , preferably 10-60%, that of the general formula II 95-0, preferably 90-40 % based on the total amount of functional

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SNSPEOTS

tional groups and in which η = 1 and R ₁ = Rp = hydrogen.

Furthermore, those synthetic resins according to the invention are preferred, the porosity of 30-60% by volume, the inner one

Have a surface area of 20-100 m / g and in which the proportion of the functional groups of the general formula III is 5-90%, preferably 50-80% and the sum of the proportions of the general Pormeünl and II is 95-10, preferably 50-10 % of the total amount of the functional groups and in which η = 1 and R = R ₂ = R, ■ = hydrogen.

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The synthetic resins according to the invention are suitable for the adsorption of metal ions and are characterized by a high Adsorption capacity for metal ions, in particular for mercury and noble metal ions, as well as by their high adsorption speed and their excellent mechanical strength combined with superior hydrodynamic Properties. In particular, they also make it possible to use them in large technical filters in an advantageous manner.

The advantage of the synthetic resins according to the invention compared with those as described in DOS 2.312.233, and even those based on a crosslinked vinyl aromatic base polymer with a microporous resin structure is based, in particular, on the fact that the synthetic resins according to the invention also have a pH value from 0 still large amounts of mercury and silver ions adsorb while the synthetic resins, the DOS 2,312,233 under comparable conditions have practically no or only a very low adsorption capacity for these metal ions. It should also be pointed out that it is possible with the aid of the synthetic resins according to the invention, for example mercury ions with high filtration speeds in one step ! Practical to completely remove this from aqueous solutions both when using a stationary filter bed as well as one Fluidized bed. The synthetic resins according to the invention are also distinguished characterized by a high level of alkali resistance. So they will for example by 10% sodium hydroxide solution only at the boiling point and only relatively slowly, attacked.

Macroporous base polymers made from mono- and polyvinyl compounds are known per se. They are produced in a manner known per se by block or suspension polymerization ier corresponding mono- and polyvinyl compounds, in contrast

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wa a compound that is a solvent for the monomers Represents mono- and polyvinyl compounds in which the obtained Copolymers, however, are practically neither soluble nor swellable. Pearl-shaped macroporous base polymers, as they are on the Ways of suspension polymerization obtained in a manner known per se are preferred. Making macroporous Base polymer is described, for example, by J. Seidel et al in Adv. Polym. Sci., Vol. 5, 1967, p. 113 ff. Compounds containing the monomeric mono- and polyvinyl compounds solve the received. Copolymers, however, neither dissolve nor swell are known per se. Examples include: gasoline Dodecane, isododecane, cyclohexanol, dodecanol, oleic alcohol and tert-amyl alcohol.

As suitable monovinylaromatic compounds that stand for themselves can be used alone or in a mixture of several, be named for example:

Styrene, substituted styrenes, such as methyl styrene, dimethyl styrene, Ethyl styrene, chlorostyrene, vinyl anisole, cC-methyl styrene and vinyl naphthalene. "._ ■"

As suitable polyvinyl compounds that stand alone or can be used in a mixture of several, for example called ·: - - r -...---.

Divinylbenzene, divinylpyridine, divinyltoluenes, divinylnaphthalenes, diallyl phthalate, ethylene glycol acrylate, ethylene glycol dimethacrylate, divinyl xylene, divinyl ethylbenzene, divinyl sulfone ,. Polyvinyl or eolyallyl ether of glycol, glycerol and pentaerythritol, divinyl ketone; JDivinyl sulfide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinate ^ diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallylsebacate, divinyl sebacate, diallyl tartrate, diallylsilicate, ni-allyl amide, triallyl-acrylate, triallyl'-methylate, triallyl'-acrylate, triallyl'-methylene, triallyl'-methylate, triallyl'-methylate, triallyl'-acrylate, triallyl ', triallyl', triallyl'-methylate, triallyl'-methyl-amide, triallyl'-acrylate, triallyl'-methylate, triallyl'-acrylate, triallyl'-methyl N ¹ -ethylenediacrylamide, 1,2-di- (cC-methylmethylene sulfonamido) -ethylene, trivinylbenzene, trivinylnaphthalene, polyvinylanthracene and tr! Vinylcyclohexane, also isoprene, butadiene,

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Piperylene, pentadiene, hexadiene, octadiene, decadiene, hexatriene, Cyclopentadiene and their substitution products, for example Chloroprene, 2,3-dimethyl-butadiene, 2,5-dimethylhexadiene, -2,5-dimethyl-octadiene.

Preferred monovinylaromatic compounds are styrene, Vinyl toluene and vinyl naphthalene, preferred polyvinyl compounds Divinylbenzene and triviny! Benzene.

It has been found to be beneficial instead of pure divinylbenzene to use technical divinylbenzene, which contains 40-50% by weight of ethyl styrene. The ones described below macroporous base polymers obtained by polymerizing a monovinyl compound with divinylbenzene, can be prepared in the same way starting from technical divinylbenzene and then contain accordingly the proportion of ethyl styrene in technical divinylbenzene in addition to units made from divinylbenzene and units made from ethyl styrene.

Macroporous base polymers are also suitable, in addition to the mono- and polyvinyl compounds mentioned above contain other vinyl compounds, such as methacrylic and acrylic compounds - especially acrylonitrile, Ethylene, propylene, isobutylene, vinyl chloride, vinyl acetate, vinylidene chloride, vinyl pyridine and substituted vinyl pyridines as well as vinyl quinolines and vinyl pyrolidone.

The amount present in the macroporous base polymer Polyviny! Compounds can vary within wide limits. In general, the content of polyvinyl compounds is approx. 1 to 50% by weight based on the total amount of monomers, a content of 2 to 15% by weight is preferred. The above Vinyl compounds referred to as additives are also generally used in amounts of 1 to 50% by weight. based on the total amount of monomers used, amounts of 2 to 15% by weight being preferred.

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In particular, macroporous base polymers are suitable which consist of 50 % to 98 % styrene, vinyl toluene, vinyl anisole or ethyl styrene and 50 % to 2 % divinylbenzene or trivinylbenzene, with macroporous base polymers consisting of 90 % to 95 % styrene and 10 % to 5 % divinylbenzene to be favoured.

If the macroporous base polymer is not already through the use of corresponding monovinylaromatic compounds contains primary and / or secondary amino groups, these are introduced into the base polymer in a manner known per se. The introduction of these amino groups into the base polymer is known; for example be here on the introduction of such Groups by way of chloromethylation and subsequent amination (USA Patent 2,629,710) or via chloromethylation and subsequent reaction with phthalimide potassium (English patent 767.821) or amidomethylation and subsequent saponification according to DAS 1 · .054.715. The introduction of such groups is also described in DP 1.045.102.

Furthermore, macroporous base polymers containing primary amino groups are obtained by nitration, for example one Base polymer made of styrene and a polyvinyl compound and. Reduction of nitration products. This type of manufacture is also known and is described, for example, in DP 1.049.583.

Another way to get primary amino groups containing macro, To produce porous base polymers is that mäh vop. uses monovinyl compounds from the start, the amino groups' contain. For example, p-vinylbenzylamine may be mentioned as a possible monovinyl compound. "'

Furthermore, macroporous base polymers are preferred that contain more than one amino group per aromatic nucleus of the base polymer and almost exclusively primary araliphatic ones Carry amino groups. They are known per se, for example by implementing the macfoporous basic

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.and; Veraeifung-der. so won; lJmseit2 ^ gsj) r ^ uk: t ^

Basic polymer © · us i »d; ^ fe ^^ iä ^ sr ^ ekaijirtfvvaörq: ifeeste Iiuiag ^ at ^ γ j for example described in DOS 2.215.956. The use of such macroporous base polymers leads, _t to the invention, high synthetic resins with "special". Capacity. ^x

r * s £> ^r

The manufacture of the; Synthetic resins according to the invention are carried out by reacting the macroporous polymer containing primary x and / or secondary amino groups with thiqcyanic acid and salts. of iniqcyansaure, ^ mustard oil or giveni | alis sub-. established. Thiqureas .:, " _r . ,. ... ... ., _,

iIfν L ..

The Umsetzimg with Thiqcya _r acid tert. or oils .Senf. occurs "in,", generally so, \ .da ₄ ß. onan, the .priiaäre.and / or the secondary amino groups, .. containing macroporous basic compounds in one, -Sus-. pensionsmittei suspended, the thio'cyansäure ^ or "the, mustard-. oil is added to the suspension and then the reaction mixture is heated with stirring. One can also proceed in such a way that one dajs. Amino group., ^{Containing.,:} Incrqpqröse Grundpplymer first, ϊμ ^ inem. ^ Fil-feerroiir _r erS; Chöpf'end .mjL ^ _: Thioeyanoic acid ..,, loaded ^; das _S q, lieladene, ma ^ op, Q ^^ ... Gip ^ dp _v ql3qae.jp _5i in ¥ aster- _r ,,, _r _ ;. _; - _T or, dilute thiqcyanic acid, suspended and .the suspension. heated with stirring.

At .rents ^
cyanic acid, 1 ^ t ₁ e ^: f ^ cli ^ aOasaasiia & iiJ ^^
Azidi ^^ _r d ^, jSimp ^ nsi ^ on; S ^ Ghfe

cyansäuaje ^ u, jwähie ^. # leimziHMiä * Minn ^ 'äSJKäi * ^ r ^ Se ^^ kls'-QV ^ I ¹ ' ³ " ³ mol / l set werjieii ^ sfb ^ spaeaisiifeisei ^ OV ^ ^ isH ^ MoI ^ aiii" ^: Thioeyanic acid, however, here the reaction products obtained. zune | men & ^ du3? cfc ^^ ^ thiocyanic acid contaminant-fc, ^ sa daiß a © - additional fteinigün ^ of the reaction ^ - products is required * -

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-ce

rs *

In the case of,; der ;: Implementation of the "g ^ ip ^ gruppen BatfealtendeniSptakriOporo ^ gn der,: · Thio_e.y. anic acid, odei ^ optionally subsrbituieyjteaa

a; -Säuare: * Tb, eis © i, e-l ^ isreiiSe ^ iner -Miaaeralsuua ^ ei, like ·, v

^^ giigani-s Meipf- | η ^ -

and the suspension under pension should not be less than 0 and at pH? Inter- Qt taiWSY- vxyr-zifgswease; izwiseheaai 2nd _; ■

lioMlä ^ S idafe2iÄiHin5ögEJirpLpen :; saatfeit endfe ί - 1 *? - 'ää,' i "-efet 'miLtiiid-eaa; b: etr? eff: end.en ^; l salt / deiitj

The response time essentially depends on the '"ffeaktxön'S'teni-" temperature and the type of base polymer used.

The amount-of = inserted acid, mustard oil odeijgegebenenfalls _{substituiertenj: t} materials depends essentially on $ the amount present in the macroporous base polymer amino groups; it can vary within wide limits

or Gege% eneM & iajs ^ kubstÄu ^ the amount of ^ Im Grian ^ th, ebeiis o ^r wi-e? men ^; About chüß an? Iühioicyansmir ef ^ c iEfeioi

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ν:

naten, thioureas or mustard oils, such as one 15-fold excess, can be used. Generally one will but with amounts of Ϊ - 2 moles of thiocyanic acid, thiocyanate, if appropriate substituted thioureas or mustard oils per mole of amino groups present in the base polymer. About that In addition, you can also use a deficit of thiocyanic acid, thiocyanate, optionally substituted thiourea or mustard oil work, whereby you get synthetic resins, the next the functional groups of the general formula I and optionally IH contain substantial amounts of functional groups of the general formula II.

The temperature at which the reaction takes place is essentially dependent on the type and structure of the primary and / or secondary amino group-containing macroporous base polymer used. In general, for macroporous base polymers with primary aromatic amino groups, lower temperatures are sufficient than for. Base polymers with primary araliphatic amino groups. In general, temperatures between 80 and 200 ^° C. are used, temperatures of 100 to 180 ^° C. being preferred.

In the case of the use of mustard oils are advantageously carried out at temperatures between 10 to 100 ⁰ C, preferably between 20 to 80 ° C. , ■

Such liquids or liquid mixtures can be used as suspending agents in question under the reaction conditions are inert to the reactants, for example may be mentioned water, methanol, ethanol, toluene, chlorobenzene and mixtures of organic liquids, such as for example ethanol-toluene or toluene-chlorobenzene.

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Preferably used suspension media are liquids, the one hand swelling agent for the amino groups-bearing macroporous base polymer and on the other hand solvent for thiocyanic acid, thiocyanates, thioureas or mustard are oils. Examples include water, ethanol and dioxane.

The salts of thiocyanic acid are generally both inorganic as well as organic thiocyanates in question, in the case of the inorganic thiocyanates in particular those with metals of groups 1 to 3 of the periodic table and, in the case of organic thiocyanates, those with organic bases how aliphatic and aromatic amines and their quaternary ammonium salts come into question. Are particularly preferred the alkali metal thiocyanates and ammonium thiocyanate. For example lithium thiocyanate, sodium thiocyanate, Potassium thiocyanate, magnesium thiocyanate, calcium thiocyanate and aluminum thiocyanate.

Examples of organic thiocyanates which may be mentioned are methyl or ethylammonium thiocyanate, benzylammonium thiocyanate and dimethyl ammonium thiocyanate.

In addition, mixtures of such inorganic and organic thiocyanates can be used. For example:

Ammonium thiocyanate / benzylammonium thioeyanate, sodium thiocyanate / benzylammonium thiocyanate and Potassium thiocyanate / benzylammonium thiocyanate.

The quantitative ratio of these mixtures is not critical and can vary within wide limits.

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Compounds may be used as optionally substituted thioureas the general formula

R ⁴

N-C-N

4 5 6
in question, where R, R - and R. ■ independently of one another for em hydrogen atom, a straight-chain or branched C -, - to Cß-alkyl radical or an aryl, aralkyl or acyl radical which is optionally substituted by halogen, hydroxy or alkoxy can stand.

Possible straight-chain or branched C ₁ -C -AlkVlreste may be mentioned, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl and amyl.

As optionally substituted by halogen, alkoxy and hydroxy Examples of aryl radicals are:

Phenyl, benzyl, naphthyl, tolyl, o-chlorophenyl, p-hydroxyphenyl and p-ethoxyphenyl.

Examples of acyl radicals that may be mentioned are acetyl and propionyl and benzoyl.

The following are examples of individual connections:

N-methylthiourea, N-ethylthiourea, N-isopropylthiourea, N- (η-butyl) thiourea, N-phenylthiourea fabric, N-benzylthiourea, N-naphthylthiourea, N-vfolylthiourea, N- (o-chlorophenyl) thiourea, N- (p-hydroxyphenyl) thiourea, N- (p-ethoxyphenyl) -thiourine-

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substance, N- (2; jA-dimethylphenyl) - thiourea, N-acetyl thiourea, N-benzoy! thiourea, N, N-dimethy! thiourea, N, N-diethylthiourea, N, N-dipropylthiourea, s-dimethylthiourea, s -Diisopropylthiourea, s-di-n-buty! Thiourea, s-diphenyl thiourea, s-ditoly! Thiourea, N, N-phenyl-tolyl thiourea, Ν, Ν, Ν '-trimethylthi oharnst off, N, N, W V-triethyl thiourea and Ν, Ν, Ν ^1- tripropy! Thiourea.

The mustard oils are alkyl mustard oils with 1-6 carbon atoms, preferably 1 to 3 carbon atoms in the alkyl radical, for example called methyl mustard oil, ethyl mustard oil, n-butyl mustard oil, n-pentyl mustard ,. n-Hexyl mustard, alkenyl mustard with 2-6 carbon atoms in Alkenyl radical, for example allyl and butenyl mustard oil, Cycloalkyl mustard oils with 5-6 carbon atoms in the cycloalkyl radical, Examples include cyclopentyl mustard oil and cyclohexyl mustard oil, optionally by methyl and methoxy radicals or halogen substituted aryl and aralkyl mustards, for example may be mentioned phenyl mustard oil, benzyl mustard oil, chlorophenyl mustard oil, Tolyl mustard oil, 2,4-dimethylphenyl mustard oil and 3-methoxyphenyl mustard oil. In particular, the use of methyl mustard oil, Allyl mustard oil, phenyl mustard oil and benzyl mustard oil are preferred.

The determination of those present in the synthetic resins according to the invention The person skilled in the art is familiar with proportions of functional groups I, II and III common. It takes place via the elemental analyzes of the used macroporous base polymer containing primary and / or secondary amino groups and reaction product obtained. the Determination of porosity and internal surface area is also available known. In general, it takes place in a manner known per se with a mercury porosimeter (porosity) or according to the BET method (inner surface), see J Seidel et al in Adv.Polym.Sci., Vol. 5, 1967, p. 113 ff.

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The use of the synthetic resins according to the invention to absorb Metal ions take place in the known manner customary for ion exchangers Way by, for example, filling a column with the synthetic resins according to the invention and aging the filled column applied to the solution to be processed. Loading can be from bottom to top or from top to bottom, just as the filter bed can be in the state of a fixed bed or a fluidized bed. The invention Synthetic resins are particularly suitable for absorbing Silver, mercury and gold ions as well as for the absorption of ions of the platinum metals. Examples of platinum metallic tones are called: palladium, platinum, iridium and rhodium. The solutions to be processed can either contain these ions contained individually or in mixtures. The concentration of metal ions in the solutions to be processed is not critical. It can fluctuate over a wide range. The same applies to the pH of the solutions to be processed.

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example 1

1000 ml of a commercially available macroporous, weakly basic anion exchanger with primary amino groups, HCl binding capacity 2.75 VaI, produced in a manner known per se according to the method of DBP 1 054 715 by aminomethylation of a 5% divinylbenzene crosslinked and by adding 65 wt. -% (based on the monomer mixture) of a Cjp hydrocarbon mixture made porous styrene polymer in bead form (porosity: 47 vol .-%; surface: 65 m / g), were in a filter tube with water and then with ethanol (technically absolute) washed until only 0.3% water was left in the drain. 1635 ml of anion exchange resin swollen in ethanol were insulated.

600 ml of the anion exchanger pretreated in this way were in ml of ethanol and then adding 109 g of allyl mustard oil (1.1 mol) heated to 80 ° for 8 hours. The reaction product was washed with ethanol and deionized water. Yield: 460 ml of synthetic resin

Content of thiourea groups: 2.14 mmol / ml. Content of amino groups: 0.1 mmol / ml
Elemental analysis: 69.15% C; 11.45% N; 12.8% S. Determination of the adsorption capacity for silver from 1 η nitric acid:

25 ml of the synthetic resin produced in this way were rinsed into a filter tube with a clearance of 13 mm and then by filtering over an excess of 1 η nitric acid preloaded (conditioned). The resin sample pretreated in this way was then equilibrated with a 0.1 η silver Load nitrate solution in 1 η nitric acid. The filtration rate was 200 ml per hour »Der FilterablauT was titrimetrically examined in portions for the metal content and the adsorption capacity of the resin from the supplied and the amount of metal measured in the filter drain calculated the silver uptake was 2.99 meq / ml resin,

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Example 2

200.ml of the in example Λ ,. used, in.Äthanol swollen, macroporous, Schwaph basic anion exchanger were in the example. 1. Specified way with 67.5 g of phenyl mustard oil instead of allyl mustard oil (o., 5 mol);. At 50 ^{o, brought} to reaction and further processed .... . ,. . ... ,, ..-.... .. - ..-.

Yield: 172 ml synthetic resin. ., ... .... ...... ..........

Thiourea group content: 1.87 mmol / ml Amino group content: 0.1 mM oil / ml

Elemental analysis: $ 72.1 6. C; 9.6. %, N; 10 _? 8 % S, the silver uptake of the resin, determined as indicated in Example 1, was .2.33.mVaJ. / Ml resin. ..... "

Example 3 ' · -. "..-..-..

1000 ml of a macroporous, weakly basic. AnionenaustausHers with primary amino groups (HCl.Bindigkeit.2,4 VaI), produced according to DP 1.054 .. 715 by aminomethylation of a crosslinked with 8% divinylbenzene and by adding 60% (based on the monomer mixture) :, a C ^ ^ -hydrocarbon mixture porp _: s made styrene polymer in bead form, (porosity: 44% by volume; surface: 110 m ² / g), were in 500 ml. fully deionized water suspended after the addition of 105 g of methyl mustard oil. (1.44 mol) stirred for 16 hours at 30 ° C. and worked up according to the information given in Example -1. Yield: -1150 ml · synthetic resin; . - ;; 7, r- -; - ■■■■ -: - ^:. · - Content, of thiourea groups: 1 * 18; mmol / ml ·; -,., - ". ■ ..-: ■ - ;: ^{Amino group content :; p ,, ^ 1} mmol / ml.:,: .. _; _ _v ;; -

The mercury intake; des-Harzes, -dur ^ carried out \ as in BeI ^ -. game 1 indicated - with eiri ^ r 0.1 n _; Mercury nitrate solution _; (in. ^^! ^, Sa ^ e ^ ferric acid) transferred · 2 »64: mVal / ml · Resin ^ _Uj - .." .. .'_... ■

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Example 4

1000 ml of the macropröseri used in Example 3 weak basic anion exchangers were made in accordance with the regulations. of Example 3 n4t 35 g of methyl mustard oil (6.48 mol) reacted and further processed.

Yield: 1175 ml synthetic resin

Content of thiourea groups: 0.4 mmol / ml Amino group content: 1.6 mmol / ml

Elemental Analysis: 77.2 % C; 9.35 % N; 3.35 % S.

Example 5

625 ml of a macroporous, weakly basic anion exchanger with primary amino groups, HCl binding capacity 1.62 YaI, produced in a manner known per se using the DP process. 1,054,715 by aminomethylation of a 5% divinylbenzene crosslinked, and by the addition of 65 wt .-% based on the monomer mixture of a Cp-hydrocarbon mixture made porous' styrene polymer in "pearl form" were in a _.._ ".. filter tube to equilibrium, loaded with about 1 31 iThiocyansäure .. After, washing the überschüssigenSäure with Waaser, 1000 mL: the so-loaded ^ ^ Anio ienaustauschers in the Thiocyanatform, isolated, SUS in 500 ml of deionized _water; pendiert and heated autoclave β h at 180 ⁰ C, iiach cooling-.the was obtained in ümsetzungsprodukt, filter tube with deionized water, 2% sodium hydroxide solution.. (until the effluent substantially free yoii thiocyanate; was ions) and then again with deionized Washed with water (until neutral flow). ■;. £ Λ "· ■.: -; .-: ... r" ■ '-

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Yield: 645 ml of synthetic resin

Thiourea group content :. 1.05 mmol / ml Amino group content: 0.6 mmol / ml
Elemental analysis: 73.9% C; 9.25% N; 8.25% S. Determination of the adsorption capacity for silver from nitric acid of different normalities (for implementation see example 1):

Loading solution:. Silver uptake 0.1 η silver nitrate in meq / ml resin

0.01 η nitric acid 1.4

0.1 η nitric acid 1.5

1.0 η nitric acid 1.65

Example 6

300 ml of the macroporous anion exchanger used in Example 5 (HCl binding capacity 0.78 VaI.) Were suspended in 450 ml of deionized water and converted into the HCl form by adding 0.78 VaI hydrochloric acid. After 30 minutes, 118.5 g of ammonium thiocyanate (1.56 mol) were added and the suspension was heated to 140 ° C. in the autoclave for 8 hours. The reaction product was treated as in Example 5. Yield: 355 ml synthetic resin
Content of thiourea groups: 1.0 mmol / ml Content of amino groups 0.4 mHol / ml
Elemental analysis: 73.05% C; 9.2% M; 8.7% S. Determination of the adsorption capacity for silver and mercury:

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a) The adsorption capacity from 0.1 η silver or mercury nitrate solution (each- in 1 η nitric acid), according to the method determined in Example 1, gave 1.6 meq / ml resin for silver and 2.34 meq / ml resin for mercury.

b) After preloading the resin with 1 η sodium chloride solution, the mercury uptake from 0.1 η mercury chloride solution was (in 1 η sodium chloride) 2.48 meq / ml resin.

Example 7

300 ml of the macroporous anion exchanger used in Example 5 (HCl binding capacity 0.78 VaI.) Were suspended in 450 ml of deionized water. After 30 minutes, 118 »5 g of ammonium thiocyanate (1.56 mol) were added and the suspension in the autoclave was ^{heated to 140 °} C. for 8 hours. After cooling, the reaction product was treated in the same way as in Example 5.
Yield: 330 ml of synthetic resin

Content of thiourea groups: 0.64 mmol / ml. Content of amino groups: 1.5 mmol / ml
Elemental analysis: 76.95% C; 9.3% N; 4.95% S.

Example 8

300 ml of the macroporous anion exchanger used in Example 5 (HCl binding capacity 0.78 VaI.) Were suspended in 450 ml of deionized water and, by adding 0.78 VaI Hydrochloric acid converted into the HCl form. After 30 minutes were 1.56 mol Kalümthiocyanat added and the suspension in Autoclave heated to 140 ° C. for 16 hours. The reaction product obtained was treated in a corresponding manner as in example 5.

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Yield: 325 ml synthetic resin, ·. Thiourea group content: 1.24 mmol / ml Amino group content: 0.22 mmol / ml: Elemental analysis: 74.4%. C; 8.4% N; 8.8% S.

Example 9 - '- ^: - "■". ■:. -. . ·: · .-

The macroporous styrene bead polymer used in Example 5 for the production of the anion exchanger was converted into a weakly basic anion exchange resin of the type of poly (aminomethyl styrene) in accordance with the procedure of DOS 2.215.956, whereby a resin was obtained which had about 1, 5 aminomethyl groups per aromatic nucleus. 290 ml of the anion exchange resin thus obtained (HCl binding capacity 0.9 VaI) were suspended in 500 ml deionized water and converted into the HCl form by adding 0.9 VaI hydrochloric acid. After 30 minutes, 137 g of ammonium thiocyanate were added, the reaction mixture was ^{heated to 140 °} C. for 16 hours and then worked up as in Example 5.

Yield: 220 ml of synthetic resin

Content of thiourea groups: 1.95 mmol / ml. Amino group content: 0.3 mmol / ml
Elemental analysis: 65.6% C; 13.0% N; 13.8% S. The silver uptake of the resin from 1 η nitric acid, determined as in Example 1, was 2.93 meq / ml. The mercury uptake was determined after preloading mft 1 η sodium chloride solution from a solution of 0.1 η mercury chloride in 1 η sodium chloride. It was 4.0 mVal / ml resin.

Example 10

1000 ml of the in example). 5 used macroporous, weak basic anion exchanger were in a filter tube Washed with ethanol (technically absolute) until the water content of the eluate was 0.4%. 300 ml of the pretreated Anion exchanger with an acid binding capacity of 0.5 VaI

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were suspended in 500 ml of ethanol and after introducing 24.5 g sulfuric acid (100%) and 76 g of ammonium thiocyanate 8 hours stirred. at 140 ⁰ C in the ^ Autoklayen. The reaction product was treated further as indicated in Example 5 .. Yields 205 ml of synthetic resin _f ■ _: -

Content of thiourea groups: 1.4 mmol / ml .. Content of amino groups: .0.4 mmol / ml ..-....,. "_

Elemental analysis: 71.0% Cj 10.1% N; 10.1% S. =

Determination of the adsorption capacity for silver and mercury (For implementation see example 1):. -.

Loading solution 0.1 η AgNO, 0/1 η AgNO 0.1 η Hg (WO ₃ ) ₂ 0.1

0.01 η HNO, ^l 1.0 η MO, 1 η HNO ^ - 1 η NaCl

- 3 3 3

Metal mount

mVal / ml Resin T, 82 2.2 2.74 2.46

Example 11 '

300 ml of the anion exchanger described in Example 10 and swollen in ethanol were washed with toluene in a filter tube until the drain was practically free of ethanol. The exchanger was then suspended in 400 ml of toluene and, after the addition of 25.0 g of sulfuric acid (100%) and 76 g of ammonium thiocyanate, ^{heated to 140 °} C. for 8 hours in the autoclave. After cooling, the reaction product was washed with ethanol and then processed as in Example 5. Yield: 200 ml synthetic resin,
Content of thiourea groups: 1.6 mmol / ml. Content of amino groups: 0.2 mmol / ml
Elemental analysis: 69.6 # C; 10.15% N; 11.15% S.

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Example 12 ,

150ml of the macroporous anion exchange resin used in Example 5 (HCl binding capacity 0.4 VaI) were in 200 ml suspended in deionized water and with 0.4 VaI hydrochloric acid in the HCl form transferred. After 30 minutes 45.5 g of ammonium thiocyanate and 66.5 g of benzylammonium thiocyanate were added, and the suspension was heated to 140 ° C. for 16 hours in the autoclave. After cooling, the reaction product was first washed in a filter tube with 1 liter of ethanol and then washed accordingly the procedure in Example 5 worked up. Yield: 166 ml of synthetic resin

Thiourea group content: 1.45 mmol / ml Amino group content: 0.2 mmol / ml
Elemental analysis: 73.55% C; 9.25% Nj 10.05% S.

Example 13

250 g of the macroporous styrene bead polymer used in Example 5 were nitrated according to DP 1 .049.583 and then reduced

150ml of the macroporous anion exchange resin thus obtained of the poly (aminostyrene) type with an HCl binding capacity of 0.22 VaI were stirred in 220 ml of 1 η hydrochloric acid for 30 minutes and after adding 40 g of ammonium thiocyanate in the autoclave for 8 hours.

heated to 120 ° C for a long time. The reaction product was after Details in example 5 processed further:

Yield: 128 ml of synthetic resin

Content of thiourea groups: 1.05 mmol / ml Amino group content: 0.6 mmol / ml

Elemental analysis: 66.5% C; 11.35% N; 6.95% S.

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Example 14

63 ml of a macroporous, weakly basic anion exchanger with secondary amino groups (HCl binding capacity 0.125 VaI) produced in a manner known per se according to DBP 1.495 * 762 by amidomethylation with N-chloromethyl-N-methyl-acetamide and subsequent hydrolysis of one crosslinked with 4% divinylbenzene and duiich addition of 60%, based on the monomer mixture, of a C ^^ - hydrocarbon mixture made porous styrene polymer in bead form (porosity: 44 vol%; surface 45 m / g), were suspended in 150 ml of deionized water, whereupon the The pH of the suspension was adjusted to about 0.5 by adding 0.25 VaI hydrochloric acid. After 60 minutes, 19 g of ammonium thiocyanate (0.25 mol) were added and the suspension was ^{heated to 160 °} C. for 16 hours. The reaction product was isolated and worked up as described in Example 5.
Yield: 59 ml of synthetic resin

Content of thiourea groups: 0.2 mmol / ml. Content of amino groups: 1.6 mmol / ml
Elemental analysis: 81.05% C; 7.15% N »1.65% S.

Example -15

1000 ml of the macroporous anion exchanger used in Example 5 were charged to equilibrium in a filter tube with 3% hydrochloric acid. After washing off the excess Acid with water was 1730 ml of that with hydrochloric acid loaded anion exchanger isolated.

300 ml of the loaded as with hydrochloric acid, macroporous anion exchange resin (anion exchange capacity 0.45 VaI) were suspended in 500 ml of deionized ^ ater and, after addition of 103 g of thiourea (1.35 IFOL) 8 hrs. In the autoclave to 180 ⁰ C. The reaction product was worked up as in Example 5.

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Yield? 230 ml synthetic resin

Thiourea group content: 1.13 mmol / ml Amino group content: 0.15 mmol / ml Elemental analysis: 74.1% C; 8.1? 6K; 8.75% S.

Determination of the adsorption capacity for silver and mercury (For implementation see example 1):

Loading solution 0.1 η AgIiO, 0.1 ^ n Ag ». 0.1 η Hg (H0,) ₂ 0.1 η H

0.01 η HiSiO ₃ 1.0 η HIiO ₅ 1, OnHNO ₃ InNaCl

Metal mount

mVal / ml resin 1.48 1.76 2.42 2.14

Example 16

1000 ml of the macroporous used in Example 5, weak basic anion exchanger with an HCl binding ability of 2.6 VaI, were suspended in 1000 ml of deionized water, and after adding 600 g of thiourea (7.9 mol), heated to 150-155 ° C. in an autoclave for 8 hours. After cooling it was the reaction product obtained in the filter tube with fully demineralized Easser, 2% sodium hydroxide solution and then again with Washed with fully demineralized water (until the drain is neutral). Yield: 1070 ml synthetic resin

Thiourea group content: 0.96 mmol / ml Amino group content: 0.6 mmol / ml
Elemental analysis: 73.95 ^ C; 8,955 ^ N; 7.7% S.

Example 17

1000 ml of used in Example 3, macroporous, weakly basic anion exchange resin having primary amino groups (HCl-binding capacity VaI 2.4) were heated to reflux (11O ⁰ C) in aqueous suspension with the addition of 1630 g of thiourea 4o Std.. The pH in the suspension was thereby increased by adding a total of 2.1 VaI hydrochloric acid a little at a time

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constantly set to 4-7 * The reaction solution was then drawn off warm and the reaction product was worked up as indicated in Example 5 : _iy / isolated iindv worked up. Yield: 1240 ml synthetic resin; .λ 3 - v content of thiourea groups: 0.46 mmol / ml content of amino groups! _L 1.4 mol / ml
Elemental analysis: 76.5% C; 9.5% K; 4.3% S.

Example 18

In a pearl-shaped syrole polymer crosslinked with 7% divinybenzene and made porous by adding 65% by weight, based on the monomer mixture, of a C 1 -C hydrocarbon mixture (porosity: 47% by volume; surface 95 m ² / g) about 1 ν35 aminomethyl groups per aromatic nucleus were introduced in a manner known per se according to the procedure of DOS 2.215.956. 200 ml of the anion exchange resin obtained in this way (HCl binding capacity 0.48 VaI) were suspended in 500 ml deionized water, converted into the HCl form by adding 0.48 VaI hydrochloric acid and, after adding 73 g thiourea, to 160 hours for 16 hours ° C heated. The reaction product was worked up in accordance with the information given in Example 5. Yield: 174 ml synthetic resin

Content of thiourea groups: 1.33 mmol / ICL content of amino groups; 0.3 mmol / ml
Elemental analysis: 68.85% C; 11.8% N; 12.1% ^C -S.

Example 19 ..

200 ml of the macroporous anion * used in Example 5 Exchangers (HCl binding capacity 0.52 VaI) were used in Suspended 400 ml of deionized water and converted into the HCl form by adding 0.52 VaI hydrochloric acid. Afterward 140 g of methylthiourea (1.56 mol) were added,.

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whereupon the suspension is heated to 180 ° C. in the autoclave for 8 hours became. After cooling, the reaction product was in the filter tube with ethanol, 2 percent. Caustic soda and deionized S. Washed with water (until neutral flow). Yield: 200 ml of synthetic resin

Content of thiourea groups: 1.58 mmol / φΙ content of amino groups: 0.1 mmol / ml
Elemental analysis: 73.4% C; 9.05% N; 10.0% S. The overabsorption of the resin, carried out as indicated in Example 1, was 2.0 mVAL / ml.

Example 20

200 ml of the macroporous anion exchanger used in Example 5 were, as described in Example 19, converted into the HCl form. After addition of 158 g phenyl-thiourea (1.04 mol), the suspension in the autoclave was heated for 8 hrs. To 160 ⁰ C, and then, vie given in Example 19, worked up.
Yield: 210 ml of synthetic resin

Thiourea group content: 1.54 mmol / ml Amino group content: 0.1 mmol / ml
Elemental analysis: 72.9% C; 9.0% N; 10.056 S,

Example 21

1000 ml of the macroporous, weakly used in Example 3 basic anion exchanger with primary amino groups (HCl binding capacity 2.4 VaI) were in a filter tube with ethanol (techn. absolute) washed until only 0.2% water in the drain were included. Then 1330 ml of the swollen in ethanol Anion exchanger isolated.

300 ml of the exchange resin pretreated in this way were in 500 ml Ethanol suspended, with 155 g (0.825 mol) ϊί, Ν'-di-n-butyl-thio-

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added urea and heated in the autoclave for 8 hours at 160 ° C-j The reaction product was, as indicated in Example 19, purified.

Yield: 235 ml of synthetic resin

Content of thiourea groups: 1.13 mmol / ml. Content of amino groups: 0.5 mmol / ml
Elemental analysis: 73.4% C; 9.2% N; 8.45% S.

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Example of distribution 1

1000 ml of a gel-type weakly basic anion exchanger having primary amino groups, prepared in a manner known per se according to the process of the DP .. 1,054,715 by aminomethylation a! Benzene crosslinked with k% Diviny, microporous styrene polymer beads were according to that described in Example 1 specified measuring period washed with ethanol. 1750 ml of anion exchange resin were isolated in the process.

200 ml of the gel-like anion exchanger pretreated in this way, swollen in ethanol and having an acid binding capacity of O:> 314 VaI, were suspended in 150 ml of ethanol and, after adding 37.5 g of allyl mustard oil (0.38 mol), heated to 80 ° for 8 hours. The reaction product was washed with ethanol and deionized water.
Yield: 156 ml of synthetic resin

Thiourea group content: 2.19 mmol / ml Amino group content: 0.2 mmol / ml
Elemental analysis: 69.25% C; 10.85% N; 11.75% S. The silver uptake of the resin was examined according to the method given in Example 1. No silver uptake was detectable.

Comparative example 2

1000 ml of the gel-like, weakly basic anion exchanger used in Comparative Example 1 and having an HCl binding capacity of 2.75 VaI were suspended in 1500 ml of deionized water. After adding 416 g of ammonium thiocyanate, the pH of the suspension was adjusted to 1.0 by slowly adding 286 ml of concentrated hydrochloric acid. The mixture was stirred for a further 30 minutes and then heated to 140 ° C. in the autoclave for 16 hours. The work-up was carried out as in Example 5. Yield: 1083 ml synthetic resin
Content of thiourea groups: 1.5 mmol / ml. Content of amino groups: 0.4 mmol / ml
Elemental analysis: 74.55% G; 8.7% N; 8.9% S. Determination of the adsorption capacity for mercury (by -

509827/0 755 Le A 15 282 _ _ZQ _

For guidance see example 1):

Preload solution loading solution mercury absorption

mVal / ml resin

0.1 η nitric acid 0.1 η mercury. <0.1

nitrate

0.1 η nitric acid

1 η sodium chloride 0.1 η mercury <0.1

chloride

1 η sodium chloride

Comparative example 3

1200 ml of the gel-like weakly basic anion exchanger used in Comparative Example 1 were suspended in 1000 ml of deionized water and, after addition of 3.3 VaI sulfuric acid (96%) and 125.5 g of ammonium thiocyanate, heated to 140 ° for 15 hours. The further processing took place according to the information in Example 5.
Yield: -1365 ml synthetic resin

Thiourea group content: 0.68 mmol / ml Amino group content: 1.8 mmol / ml
Elemental analysis: 78.45% C; 8.95% N; 4.35% S.

The mercury intake, carried out according to the information in example 1 with a solution of 0.1 η mercury nitrate in 0.1 η nitric acid, was 0.4 meq / ml resin.

Comparative example 4

In polystyrene pearl polymer cross-linked with 2% divinylbenzene about 2 aminomethyl groups per aromatic nucleus were obtained in a manner known per se using the DOS 2.215.956 method introduced.

236 ml of the gel-like anion exchange resin thus obtained

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(Hßl binding capacity 0.73 VaI) were suspended in 400 ml of deionized water, converted into HCl form by adding 0.73 VaI hydrochloric acid and then heated to 140 ° C. for 16 hours after adding 111 g of ammonium thiocyanate. The reaction product was isolated and worked up as indicated in Example 5,
Yield: 150 ml of synthetic resin

Thiourea group content: 2.7 mmol / ml Amino group content: 0.8 mmol / ml
Elemental analysis: 63.85% C; 14.3% N; 14,1556 S * Determination of the adsorption capacity for mercury (for implementation see example 1):

Pre-loading solution loading solution

Mercury absorption mVal / ml resin

0.1 η nitric acid 0.1 η mercury

. nitrate '<O ₉ 1

0.1 η nitric acid

1 η sodium chloride 0.1 η mercury chloride <.0.1

1 η sodium chloride

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Application example 1

Determination of the breakthrough capacity for mercury in the fixed bed filter ?

1000 ml of that prepared according to Example 6 were used for the experiments Resin used in a glass filter tube. The layer height of the resin filling was 71 cm. The top of the resin The solution conducted had the following composition: 500 ppm Hg (as mercury chloride), 1000 ppm sodium chloride and hydrochloric acid different concentrations (see table) was 7.1 m / hour. The mercury analyzes were carried out according to the method of flameless atomic absorption spectroscopy carried out.

The breakthrough capacity (mercury absorption in g Hg / 1 resin) was determined for 3 pH settings and 2 breakthrough points (mercury content in the drain):

pH in the feed j 1 5.5 10 1 ι 10 1 1 10 Hg content in the process in ppb Breakthrough capacity 155 165 142 152 141 150 / g Hg / 1 resin]

Application example 2

Determination of the mercury slip when loading according to the fluidized bed method:

In the same apparatus as described in the above application example 1, 1000 ml of the prepared according to example 6 were Synthetic resin with a mercury solution of the following composition: 5 ppm Hg (as mercury chloride), 10 ppm sodium chloride, pH 5-6. The filtration rate was

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initially set to 7.1 m / hour, the total amount of resin forming a fluidized zone, and increased to 10.6 n / hour after 70 hours. The experiment was terminated after a further 120 hours. During the entire running time, no mercury was detectable in the filter drain (mercury slip <1 ppb).

Application example 3

Determination of the breakthrough capacity for gold in the fixed bed filter ι About a 10 ml sample of the resin prepared according to Example 10 was placed in a glass filter tube, a 0.01 η solution of tetrachloroauric acid in 1 η hydrochloric filtered "(1, S7 g Golc / 1 solution. The layer height of the Resin filling was 11 cm, the filtration speed 2.2 m / hour. The breakthrough capacity of the resin was determined for a gold slip of 1 ppm gold in the outlet and 200 ppm (approx. Λ0% of the gold content in the inlet). The values were 143 mg Au / ml resin or 236 mg Au / ml resin.

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Claims (1)

Claims 1. Synthetic resins made from a crosslinked, macroporous vinyl aromatic. Basic polymer made of mono- and polyvinyl compounds, the one. Pore volume of 20 - 80 Voi .- ^ s, preferably 30 - 60 YoI .- ^ and an inner surface of 10-500 η / g, preferably 20-200 m / g and of its aromatic nuclei at least 10 % by a maximum of three functional groups of the general formula 1-3), II. P _f
and / or ^L * "" - '(1-3) are substituted per nucleus, where P ₁ an aromatic core clbs iakroporSsen 2-ri.nd- ; polymers, η is an integer between 0 and 2. R., R ^ and R ^ are the same or different and unach'äng- . . . ig from each other a "/ia.ssers~Z-.za.zzzL, a straight cextile or branched CC ^ -alkyl-, & 2 ~ £ μ ~ alkenyl, a C ₌ -3 ^ -cycloalkyl radical, optionally substituted by C.-C ^ -alriyl, alkoxy or halogen denote aryl or aralkyl radical, ρ one of p. different core of the isacrcporous base polymer, and where ± ~. ^ p. ± le of III = 0 and R = ¥ assersxofx the proportion of I 5 - 100 73, that of II 95-0> =
in the case of III = 0 and R ₅ , = R ^ = hydrogen the portion of I 5 - that of. II 95 - O % ₅ , ^ Ö -33- BADORlGlNAt 509827/0755 and in case III not equal to C-. - .the portion of I 1 - 95 %, - preferred v / cis = 'C - £ 2 of II 98-4 $ · ί ,. preferably .55 - .'- r- '- "-. of III" 1. - 95 yi, preferably 5 - 52; - on the sum of the functional groups: e: rar *. 2. Synthetic resins according to claim 1 with a macroporous base polymer of 50-99 % by weight, preferably 85-98% by weight of Koiio vinyl compounds and 1-50% by weight, preferably 2-15% by weight. Polyvinyl compounds. 3- synthetic resins according to claim 1 and 2 with a macroporous Grundpplymer of 50 - 99 wt .- ^, preferably 85 - 98 wt .- # styrene and 1 - 50 wt -. ^, Preferably 2 - 15 wt .-% divinyl benzene. 4. synthetic resins according to claim 1 to 3, in which the proportion of the functional groups of the general formula I 10 - _f 60% 'of the general formula III range 5 - 80% and of the general formula 85 to 10%, based on the total amount of functional groups. 5. Synthetic resins according to claim 1 to 3 with a porosity of 30.-60% by volume, an inner surface of 20-100 m / g, in which the proportion of functional groups of the general formula 15-100, preferably 10-. 90%> that of the general formula II is 95-0, preferably 90-10 % based on the total amount of functional groups and in which η = 1 and ^R i '= R ₂ S = hydrogen and R 1 is methyl ,, Phenyl, allyl or benzyl. · -. -; 6. Synthetic resins according to claim 1 to 3 with a porosity of ^{30-60 vol .-%, an inner surface of 20-100 m 2} / g, in which the proportion of functional groups of the general BATH ORIGINAL .. ':. ; - & 09827 / O755 V Formula I 5-100, preferably 10-60 %, of the general formula II 95-0, preferably 90-40 % based on the total amount of functional groups and in which η = 1 and R ₁ = R ₂ "= R ^ = Is hydrogen. 7 · Synthetic resins according to claims 1-3 with a porosity of 30-60% by volume, an inner surface of 20-100m ² / g. in which the proportion of the functional groups of the general formula III 5 - 90%, preferably 50 - 90% and the sum of the proportions of the general formulas I and II 95 to 10, preferably 30 - are 10% and η where = 1 and R ₁ = R = R = hydrogen.
² 3 _ § Process for the production of thiourea groups containing Synthetic resins, characterized in that crosslinked macroporous ones containing primary and / or secondary amino groups vinylaromatic base polymers in the presence of a suspending agent with thiocyanic acid, thiocyanate, optionally substituted Thiourea or a mustard oil, at an elevated temperature implements. . 9. The method according to claim 8, characterized in that one uses macroporous base polymers of styrene and divinylbenzene. '· - ■ "■ 10. The method according to claim 8 and 9, characterized in that macroporous base polymers are used which contain more than one primary amino group per aromatic nucleus. Le A .15 282 - 35 - 509827/0755 11. The method according to claim 8, characterized in that one used as suspending agent water. 12.Verfahren according to claim 8, characterized in that nan 'Dioxane is used as a suspending agent. 13. Use of the synthetic resins according to claims 1-7 for adsorption of mercury, gold, silver and platinum ions from their solutions. · Le A 15 282 - 36 - 50 98 27/07 55