DE2447305C3 - Process for the production of chelating polymers - Google Patents

Description

(CHR) _n COOR "

in which R 'is hydrogen or a methyl group. R "is an alkali metal or an alkyl group with 1 to 4 carbon atoms and η I or 2. At least / wci active hydrogen atoms bonded to the nitrogen atom must remain in the molecule, with diepoxide compounds, optionally in a solvent, subjected to a polyaddition reaction, in a second Reaction stage the product obtained is cured by adding known epoxy resin hardeners to a product with an epoxy group, the dicpoxy compound being set in a molar excess in the first stage or the prepolymer by a molar excess of poly-N-substituted polyamines or poly-N- siibstituicrtcn polyalkylenimine is cured, and in a third stage the cured polymer or the cured prepolymer of the second stage or the reaction product of the first stage, if the N-substituent of the poly-N-substituted polyamines or poly-N-substituted polyalkylene a carboxyalky l or a cyanoalkyl group isi. is subjected to acidic or alkaline saponification.

2. The method according to claim I. characterized in that the dicpoxide compounds are 1,3-bis-11.2-epoxy-prop · xy) -ben / ol. 1,4-bis (1,2-epoxypropoxy) ben / ol. 12 - bis (p - 1.2 - epoxy propoxyphenyDpropane. N.N'-bis (2,3-ipoxypropyl) piperii / in. Ll »Fiisfp- Ι.2-ΙίροχγρΓοροχγρΗειι> Ί) -2,3-ρΓπ-pandiol. Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. Cilyeerindiglycidyl ether. ! Vntaerytiiril - diglvcidvläthcr. Sorbitol - diglycidyllithcr. Polväthylcnglykokliglycidv lather. ΙΌΪ \ - prnp \ leiigl>koldigl>ciil> lather. Vinylcyclohcxeiidii>\> il inni or diiladicudioxul can be used.

V The method according to claim I or 2. characterized • jekcnn / eichiiel. dal / ur production of the chelal

forming polymers in the form of powder or spherical particles the polymerization mixture in an aqueous solution of a water-soluble polymer or a nonionic polymer Poured surfactant and the resulting slurry by adding Epoxy resin curing agents are cured in the aqueous solution.

4. The method according to claim 3, characterized in that as an aqueous solution of a polymer, into which the polymerization mixture is poured, one of carboxymethyl cellulose, Polyvinyl alcohol, polyvinyl pyrrolidone and polyethylene glycol (molecular weight 400 to 6000) and those with a polyoxyalkylene group are used as nonionic surface-active agents will.

The subject of the invention is a method for Production of chelal-forming polymers for the

:> multiple, cheap and effective removal of unwanted Schwcrmctallioncn from industrial wastewater, such. B. Sewage from the mining industry, electrolysis, wire production, semiconductor production, plating, catalysis, fiber,

to pigment and dye production as well as scarring and similar industries, the precipitated or adsorbed heavy metal ions also can be easily recovered. The founding Procedure leads to chclatbildcndcn

) ■ -, polymers through which the Schwcrmclallioncn can be easily recovered. In particular, this gives chclalhildcndc polymers, those with harmful heavy metals, such as /. B. with mercury. Cadmium, zinc, copper

• in and lead. Enter into reactions, whereby the heavy metal ions precipitated or adsorbed and easily recovered from the chelating polymers can be.

Up to now, polymers were used as chclalhildcndc

π Removal of heavy metal ions, slyrole-divinylben / ol mixed polymeric resinsc with an iminode acetic acid group

IN (CIi.COOH) ₂ )
κι or polyamine group

((NHCIbCH ₂ ) J ONH ₂ )

and resins of the thiourea type or dilhiocarbaiic acid resin, produced by incorporation in

■)> resins of a sulfur or Slieksloff group, the opposite Heavy metals are known to have a greater affinity. For the production of chclat-forming There are a number of publications for polymers in general (Sadao Yo s h i k a wa, Yuki Go-

Wi sei Kiipnkii, Organic Industrial Chemistry II, 40? (l '). \ 1): losei Il ο jo. Kogyo Kagakti Zasshi, Journal of Industrial Chemistry ViI. 77S [1 «58 |; Makolo (liüinarii. Yuki (iosei Kagaku, Organic Industrial Chemistr \ IS. 229 [1960]; Rudolf Hering.

hi »Chclalhildcndc ion exchanger« Akademie-Verlag, Merlin (19671: Functional High Polymers, Kobimshi .1 i k k c η g a k u. I ΙίμΙι poK mer Experiments 7. 29 91 I 1974 |). Chclalhar / e des iminodiacetic acid!) Ps «in-

the one made from m-phenylene glycol salt and formaldehyde manufactured (H. P. G r e g ο r, M.Ta i Te r, L. C i t a r e I, E. I. B ac empty, Ind. Eng. Chem. 44, 2834 [1952]), and later the production of chelate resin by introducing an iminodiacetic acid group (Mukolo Oga wara, Yoshiaki Yo η eda, Eiji I mo t o, Kobunshi Kagaku, Chemistry of High Polymer 17, 30 [I960]) or a polyamine group (K. W. P e pper, H. M. Paisley, H.A. Young, J. Chem. Soc, 4 (W7 [1953]) in slyrole / divinylbenzene copolymer reported.

Then one comes to chelate resins of the polyamine type, by introducing a polyamine group into a styrene / divinylbenzene copolymer, which also has Monochloroacetic acid can be acetylated to a chelate resin of the iminodiacetic acid type (Yujiro Kosak a, Akihiko S h i m i ζ u, Toyo Sodaho- Peports of Toyo Soda Co. - 2, 206 [1958]):

Reaction (I)

NaOH R-NH-C ₂ H ₄ NH-C ₂ H ₄ NH · ■ · + ClCH ₂ -COOH ► products

R - N - C ₂ H ₄ - NC ₂ H ₄ N · · ·
CH ₃ CH, CH ₂

COONa

COONa
COONa

(R: resin)

Resins of the aminocarboxylic acid type produced by reacting epoxy groups are also known containing aminocarboxylic acids with a polyamine or a polyol (reaction II)

-(Polymer)

Polyol I.

CH ₂ -CH-N- (CH ₂ COOH), * 0-CHn-CHN- (CH ₁ COOH),

O OH

and epoxyethylethyldiamine-diacetic acid-Har /. produced by the polymerization of epoxy derivatives (reaction 111)

CH, - CH- NCH ₂ CH, NH

CH, - COOH

CH ₂ -COOH

However, these plastics have low and low heavy metal ion adsorption / exchange values Adsorption rates (exchange). From an economic point of view, these are Polymers are expensive, and once adsorbed eye metal ions can only be removed again with difficulty. Recently the reactivity of a mercapto group has been pointed out and it has been suggested that chclal-forming To produce polymers by incorporating a mercapto group into cellulose. Although this Plastics are actually attractive, they are only in the laboratory test stage and have been not yet used in practice.

We have now found that a water-soluble oiler insoluble polymer with at least two tertiary Amino groups and at least one carboxyl group in the molecule are effective for recovery and recovery can be used by heavy metal ions, read more, the polymer has a greater affinity for metal ions. so there better chelation is obtained. The llar / can also be used as a dye. Anti-static binder Means in Sviiihei Fibers and Art CH, -CH

N-CH ₂ -COOH

CH,

CH,

NH CH, COOII

fabrics, electrically conductive plastic, fogging of glasses preventing agent and similar like dispersion agent! and the filling promotional agent can be used. A water-soluble plastic of said type can be used as a rust preventive. Latex auxiliaries. Thickener. Swelling agents and used for similar purposes. The plastic of the invention can be briefly summarized by the following three-ring reaction:

In a first stage, they are carried out in a solvent or in a solvent-free medium poly-N-substituted polyamines or poly-N-substituted Polyalkylenimines, which are obtained by substituting the polyamines or polyalkylenimines on the nitrogen atom active hydrogen atoms located by, alkali metal salts or. Mk y lesler of a Ca rhi > \> alkyl or a cyanoalkyl group are obtained, where at least two akli \ e. to the nitrogen atom bound hydrogen atoms should remain in the molecule, mil liiepoxuherhindungen a polyaddilion reaction subject.

In a rapid reaction stage, the result will be achieved Product by / iisalz hckaunler I larliingsinillel fin

Epoxy resins to form a plastic with an epoxy end group cured, the diepoxy compound used in a molar excess in the first stage is, or the prepolymer by a molar excess of poly-N-substituted polyamines or poly-N-substituted polyalkylenimines !! is cured.

The third stage comprises an acidic or an alkaline saponification of the hardened plastic or of the hardened prepolymer of the second stage or of the reaction product of the first stage, if the N-substituent of the poly-N-substituted polyamines or the poly-N-substituted polyalkyleneimines is an alkyl ester of a carboxyalkyl or a cyanoalkyl group.

The process according to the invention for the preparation of chelating polymers is characterized in that that poly-N-substituted polyamines obtained from polyamines of the formula

R —NH! RNH!, H

wherein R is hydrogen or a Alkvlgruppe with I to S carbon atoms or egg nc / I H ydrow alkyl group having 2 to 8 carbon atoms. R 'an ethylene. Phenylene or xylylene group and η I or, or poly-N-substituted polyalkyleneimines, from polymers of ethylenimine. 2-methylethylamine. 2-Ethyläthyienitnin. 2.2-dimethylethylnimine. cis- or trans-2,3-Dimethyläthylcnimin ode. Copolymers of Athyicnimin and N-substitiericnÄthylcnimincn obtained by substitution of the active hydrogen atoms on the nitrogen atom of the polyamines or polyalkylenimines by alkali metal salts or alkyl esters of a carboxyalkyl or a cyanoalkyl group, the N-substituent being a cyanoalkyl group of the general formula

(CHR ¹ I _n CN

in the , '·.' Hydrogen or a methyl group and / ι I or 2, or the alkali metal salt / or the Alkyleslcr a carboxyalkyl group of the general formula

(CIIR) _n COC) R "

in the ti ' hydrogen or a Mcthy! group. R 'is an alkali metal or an alkyl group with 1 to 4 carbon atoms and I or 2 is. where at least two active hydrogen atoms bound to the nitrogen atom must remain in the molecule, with diepo \ yd compounds. optionally subjected to a polyaddition reaction in a solvent, in a while reaction stage the product obtained is cured by adding known epoxy resin hardeners to a product with an epoxy end group, the diepoxide compound being used in a molar excess in the first stage or the prepolymer through a molar excess of poly-N-substituted polyamines or poly-N-substituted polyalkyleneimines is cured, and in a third stage the cured polymer or the cured prepolymer of the second stage or the reaction product of the first stage, if the N-substituent of the poly-N -substituted polyamines or poly-N-substituted polyalkylenimines an Al-

in kylester of a carboxyalkyl or a cyanoalkyl group is subjected to acidic or alkaline saponification.

The reaction in the second stage can be carried out by either of two methods described below will:

1. Formation of the plastic obtained in the first stage into a film and curing of the Films. This film can be used as such

JIi become, or else he v, .. 'j to a piilvcr-

shaped or granular cured product Processed with suitable grain size.

2. The plastic obtained in the first stage is heated into an aqueous solution

2> one or more water-soluble plastics

or non-ionic surfactants poured to obtain such a slurry.

The hardening of the plastics is in the

made in slurry so that a cured powdery or granular plastic of suitable grain size is obtained.

The second method described above for hardening through the use of water-soluble plastics

r, substances or non-ionic surface-active substances a cured plastic with a particle size of between 4.7 and 0.05 mm or finer is obtained. the Particle size can be handled without any special requirements can be set.

4 (i The method according to the invention is distinguished characterized by particular simplicity. The polymers produced in this way have a high ion exchange rate with respect to various heavy metal ions as well as a pronounced selectivity, whereby

4-, it /. B. is possible. Traces of a specific heavy metal ion to be removed selectively and completely from an aqueous solution by adsorption without further melallions. which are present in greater concentration, are precipitated. The insoluble art

, (I substance can contain high amounts of various heavy metal ions adsorb, the plastic also has good properties in terms of chemical resistance especially to alkali, and resistance to shock, can easily be

j-, movies. Kugcl ^r ormcn or powder are formed and formed according to the following reaction IV:

CH, CII R CH ΠΙ. ι Nil -CH, dl, - NII

O O Cll · COOR CH, COOR

Polyaddition saponification

(NaOHl

N (II; CH, N Cl l _: CH R ¹ CH CII,

CII; Ul, OH Oll

COONa COONa

wildly explained the LiTuulung even further.

In a first line, polv-N-siihsiiuiierte PoKa mine or poK-N-su bsi iluierle PoK alkylenimine with lines ¹ - / white iikli \ en. in a sticky sticky water loaf with dicpovuKerhinilungcn in a loosening mill (which facilitates stirring, and improves the physical adsorption of proteinaceous ions through the porosity of the plastic produced, which is subsequently hardened), or The nature of a solvent was brought to a temperature of between 50 and 150 C for up to 15 h / in reac lion.

IOK-N-subsiiIiiicrIe polyamines or poK-N-subsiiliiierle Polvalkv lenimine with at least / white active W assei slollalomen. In a slick slipper. those who can be cingesel / l in the first section of the present i'.riiiuiung include Aihy lendiamiiiediacelcnilril. Alhy lend ia mine - dipropionitrile. .ΛιIiν lendianiinculi -12 - η ie lh y I pro pic nil π 11. I'rc ρ ν I ei idia η ι in ο d! Acetonitril. I'ro ρ ν lend la mi no - propioiulril. I'rc ρ ν lcndiamino-di- (2-mcthv lpiopionilrill. I leva me I h ν leiidianiinod! Acetonitril. I levamelhy lendiamino - dipropionitril. 11L "va mel h ν lend ia mi I) c - dil2 - met hy Ipro ρ icnil rill, mX ν loldianiincdiacelcnilril m-Xv ICID ia mineili ρ rc pic ni ι i'il m-Xv loldianiino-dil2- melllv I - pi iipionilrill.:. 11 ml Alkalimclallsal / e or Alk lesler ν l ( ', C ₁ I \ on Λ lh ν lend ia mi no - d! Acetic acid. Alliv le ndia mi no dipropionic acid. Athv leiidiamuio - ili -11 - melhν I - propionic acid !. Λ1 Ii ν I ei id ia mi Ii c-ti i -12 - mel h ν I - propionic acid !. I'rcpv leiulianiino - diacetic acidc. i'rcpv leiulia in inc - ti i per pic η acid.I'rcpv leiul in mine - tlil I - methv l-propionic acid. I'rcpv lendiamine -12- nictliv I -prcpionic acid. I levamelhy lendiaminodiacetic acid. I levamethylenediamino ■ dipropionic acid. I levainelliy lendiaminc-di - {I - never! In I - propionic acid !. I leva met Ii ν lentlianiinc-l2-methv I-propionic acid), ni-propionic acid -.Xy loldiaminotliessiiicäure. In - XvlcKliami nc - diprcpicic acid. m - Xvloldiamino - di - Il - niethvl - prcpicnsäurel.

οι - V \! .- 1.1 ti ηιίιι, ΐ _ <li -1 "* _ nii'lh \ I - , \ ιηΐΊ» nii ui ^ u 11 rr ¹ 1 and by C'vancalkvltiruppen. ie KIIR I ₁₁ CN Iwobei R iileich Il otler Ci \ _x is uiul ii a / aiii / between I and 2 represents!

KHR I _n COOR

I where R is a water sioffaiom otter ClI ,. η a / ahl / between I and 2 iiiul R a Mkalmielall ciler a hydrocarbon term: ppe with I to 4 carbon atoms! from N-Alkvlälhvlendiamni. N - Aikv I - propvlentliamin. N - \ lk \ Ihevamethv lendianiin. N -Alkvl- m- wloldiamine. N -AlkνI -tliäthv len-! Rianiin. N-Mkvl-iriälhvlcn-lctramin. N-Alkvl-ietraäih \ lcnpcii! Aniin. N-Alkvl-pcnlaathvlenhcvaniiii. Dieth \ ientriamine. Tnälhvlenletramin. Tciraalln lenpeniamine. Fcnlaäthvlcnhcxamin. Pohäihvlcnirnin. PoIv-12-methv I-älhv Icnimin). PoIv (2 - äthv I - äth \ len iniin I. PcKl2.2-diniethvl-äthvlenimin iiiul Pol ν (eis-2.3-dimethvl-üthvlcnimin). As poly - N-substituted PcIvalkvlenimine. Those from mixed polymers of N-substituted Athvlenimin Athvlcnimin are obtained, the PoIv merisaic of the following compounds can be enumerated: Athvlenimin with N-Cvanomethvläthvlenimin. Athvlenimin with Mcthvlestervon N-Athνlenalvein.

The 1 rlinduiiL ¹ lsi of course not .ml the above-mentioned pel ν -Ns exercise itiiici len PeIv a mine and pely-Vsiihsiituierlen PoKaIkylciiimine limited the weller above mentioned Mkvlgruppe look! from a range of 1 to 5 carbon atoms or an ivdrcvyalky group with 2 to 5 carbon atoms diepovy divisions. the n of the icy mare will get to know, unilet:

1.3-His- (1.2-1 -pe ν ν ρ ro pe ν ν iben / ol.

1.4-His-l 1.2-1 pev \ prope vy iben / el.

2.2-His-Ip-1.2-1 pe ν ν pro pe vy phen ν 11-propane.

N. N -His-l 2.3-1 -pe vv ρ ropy Il pipera / in.

A't h ν len iil ν k old ig Iy cidy lather.

I'ropy leng Iy k old igly cidy lälher.

I'entaeι y ιhritdigK cidy lather.

(ti ν cer md ig I ν citl y lather.

Soi'bildiiiKcidy lälher.

Pelyäihy lengly koliligly ciily lather.

Poly propy leiiglyk old igIy cidy lather.

I I -His-lp-1.2-1 pe ν y pro pe ν y ph η ν 11- 2.3 -pie pa n-

tliol.

Vi ην lev cle he valves ν y ti and Γ.ιι lad lend lev vd

) ie above I) iepovyiKei bmdungeu can All or in a mixture cingescl / l are the LiTmtlung isl flour on the top egg wälinlen Diepovytl- \ er bi ι iil ii ημ · ..-. ι limited.

Organic solvents that work in animal silence / H. Hen / ol. linseed oil. Xylene. Hulvlenglv kolmonobuly lälher. Ethanol. | sopropy !alcohol. Dimelhy Ifcrmamiil. Dimelhν Uulfovyd. N-Mel Ii y I pyrrol itlou. The van. I 'el räch Ic rk eh lens! oil. Chloroform, n-llevan and cvclelievan. These kiinnen only otler can be used in a mixture, / usät / lich water can also be used as a solvent

The hardening of the plastic can according to one tier / '.'. in leading proceedings:

1. The plastic material obtained from the first step is processed in a LiIm which is released at a temperature between W) and ISII C during j nis 24 suilkieii iti «in! iiciü. ·. in ¹ I V ^, a first Slufe solvent was milverwentiet, the curing under Lutfernen ties Lösiiiiüsiniiieis ν orgcnomnieni is.

2. The plastic obtained in the first stage is heated to a temperature with stirring and Lrvvärmeii / wipe M1 and IOD C in an aqueous solution of an oiler of several water-soluble polymers or cast non-toxic surfactants, so that animal plastic in the aqueous Phase up! becomes and spherical cured particles of a uniform particle size are formed. The curing / eii bciiagi 5 to 3 "hours.

Häriungsmiitei for L.po \ ydhar / e. which are in the /v> Stage 'inucset / t can include diethylenetriamine. Triethylenetetramine. Tetraethylene pentamine. Ethylenediamine. m-xylcldiamine. m-Aminoethy Ipipera / in. m-phenylenediamine. Diaminodiphen ν 1 methane. Diamine diphenyl sulfone and phthalic anhydride. Water-soluble plastics that can be used as a medium include carboxymethyl cellulose. Polyvinyl alcohol. Polyvinylpyrrolidone and PoK-ethylene glycol (Molecular weight 4CXj to 6000). Non-ionic surface-active agents with a polyethyl group or polvoxypropylene group are cinnamon.

In the third stage, m> proceed, dal.! if in the first stage pol \ -N-substituted Pohamine or poK-N-MihsiiiuieriL · Polyalkylenimines, which as N-Subslituenl a C \ anoalk \ lgruppe or an Alkvlesler to trust a Carhow alkvl group, to be deployed, the linear plastic from the first stage with a suitable amount of a permanent alkali solution or A mineral acid | 5 to 30 (iew. "ni at a low temperature / between fid and H) (I C are saponified for 1 to 5 hours, so that in most of them lall We obtain water-soluble plastic.

The hardened ll'estel plastic that is in the

10

/ broad stage is obtained in an aqueous Alkalilösuiiü or a mineral acid solution II to 20 (jcw. "<> | At a temperature / between W) and 100 C for 1 to 10 hours so that it is soaped water-insoluble plastic is obtained.

The reaction between the methyl ester of metin lenediamine propionic acid and a diepowd compound in equimolar amounts, as will be seen further below, can be shown. Since equimolar Amounts of each reaction component are used, the curing in the / broad stage omitted.

First stage reaction (equimolar reaction)

\ ll (M, CII: NH I (II, to R CII

CII; CII; O

ClI, COO (H, CII; COOCH, CW ₂

Pole addition reaction

j N CII; CH; N CII; CH R CH CH;

I (II; CII; Oil OH

(Il COUCH, ClI; COOCH,

Reaction in tier third stage

NaOII
Saponification

(H; CW, NC II, CH R CW CH, j

(H; CII; OH OH

CH, COONa CII, COONa

Sundays can be done as above. water soluble or -insoluble chelating plastics easily and be manufactured cheaply. The chelating plastics can possibly be used to remove harmful heavy metal ions from industrial Ah- ■ Λϋ-, ΝΟΓϋ sow ': · / n- W iodergewinnunti such heavy metal ions get emgesei / t. The synthetic fibers produced in this way can also be used in Karben. Bmdjirntteln. electrically conductive plastics, the eleklro-latisehen charge counteracting Mii-JcIn. refractory means. Ionic films and lo'ien exchange fibers are used.

For a better understanding of the invention, reference is made to the following examples, in which the parts and pro / entangabcn on the dew ich! relate.

Example I.

50 parts of ethylenediamine - dilmethv Ipropionatl. ⁷ 3.2Teile 2.2-His-Ip-Li-I-POWPrOpOWnIIeIi) I) PrOPaU and 50 parts of toluene were subjected to a l'ohadditionsrcaklion in a slick material stream at a temperature / wipe .SO ¹ and X) C for 4 hours. After this reaction, the. Product of 60.2 was! 'Rush of an aqueous 30 "" sodium hydroxide solution at a temperature / wipe SO wud K) OC for 2 hours \ erseift. Water. Methanol and toluene were distilled off. The resulting Polvmerisat was evaporated under reduced pressure dried, purified Aceion medium vVasser-by repeated Ausfaüimi! a and again under reduced pressure 'dried. The yield hetruü ^l) 4.5 "n. Of the

resulticrcntlc plastic was a water-soluble, stayed, hard powder. Her plastic had a nitrogen content of 4.6K%. determined by the Kjcldahl method. on (calculated 4.76%).

.!. () u of a 15% η aqueous solution of the plastic were each 2 l of an aqueous copper sulfate. Calcium sulphate. Lead nitral or mercury chloride solution added (Austiangskonzentratioi 20 ppm). After shaking for 5 minutes, the precipitate was filtered off. By means of the atomic absorption spectrum of the filtrate it was found that the copper ions, ¹ % of the admiumioncn. 99.5% of the lead ions and 7.6% of the mercury ions had been removed.

Example 2

100 parts sodium ethylenediamine diacetate. 220 parts ll-bis-lp-l, 2-epoxyphen \ l) 2.3-propaiKliol (Lpoxydäi'i :: \ ale:; t: 2! 9.!) * IüvJ 300 ":; water» uuden · Αν. ·; γ subjected to polyaddition reaction in a nitrogen stream at a temperature between 50 ° C. and 90 ° C. for 5 hours After completion of the reaction, the resulting aqueous solution was poured into a large amount of acetone (7 to 10 times the amount of the solution) to precipitate the plastic Plastic was separated off and dried under reduced pressure. By dissolving and precipitating the plastic twice from a water-acetone medium, the plastic was cleaned and again dried under reduced pressure. The yield was 80.5%. The product was a viscous, white and water-soluble plastic The nitrogen content, determined by the Kjeldahl method, was 4.12 "(calculated 4.32%).

3.0 g of a 15% strength aqueous solution of the plastic were used to pinch copper and lead ions as described in Example 1. 65.2 "n of the copper ions and 72.3% of the lead ions have been removed.

Example 3

50 parts I le \ amelh> lciuhamiudipropionilnl.

32S.3 'file PolyäthylcnglykoIdiglyckh lather II-po \ ydequivalent: 265.0) and 50 parts of ethanol underwent a polyaddition reaction in a Siicksloffalmosphäiv subjected at a temperature between 70 and SO C for 1.5 hours. After the reaction has ended the product was filed with 3W) of a 10 "strength aqueous sodium hydroxide solution at a temperature between SO and 100 C for 4 hours. until no Ammoniakgerueh ι ,, or was noticeable. After completion the saponification was slowly a 5% hydrochloric acid at a temperature between η 50 and 60 C see added until a pH between 6.5 and 7.0 is obtained became. The precipitated plastic was filtered off. washed with water and under \ encouraged Print dried. The plastic became 2 χ from -inem \ ceton-DMl · 'medium precipitated, so that a polymer read acid et) ps was obtained. The product obtained was a lingering, soft Kimslstoffpul'.cr. The yield was 84.5%. The nitrogen content was 2.75%! Calculated 2.N6% I. Plastic was in a suitable amount of a 5 "« strength aqueous sodium hydroxide solution at a temperature between 70 and SO ("dissolved, and the water was distilled off. After drying under reduced pressure, a polymer in Na 'form in the form of a white, get hard puhers. 2.6 2 of a 15 "< > ition wassriun Solution of the plastic were, as described in Example I, for the removal of copper and cadmium ions used X9.4% of the copper ions and 90.2 "11 tier (admiiimionen thus from the Solution removed.

Example 4

20 parts of ethylene diamine diacetonitrile and 12.5 parts of butadiene diowd were placed in an autoclave and reacted at a temperature between 70 and 75 ° C. for 4 hours. After the reaction had ended, the product was saponified at a temperature between 50 ° and 100 ° C. for 4 hours with 11.5 parts of a 10 "strength aqueous sodium hydroxide solution. In this way, a polymer of the acid type as described in Example 3 was obtained Plastic consisted of a soft, brittle powder. The yield was ¹ ) 1.5%. The solid material was 10.45% (bere '.'H'Hi 10.6X% 1 treated further as described in Example 3, so that a polymer in Na 'form was obtained The polymerisation product was a white, hard powder.

The method \ on Example I was repeated with the Unterschied.daß 1.4geiner I5% aqueous solution plastic ties were used to copper ions and Cadmiimiionen / u remove. An inlucation of 45.3% for copper ions and 47.1% for admiuniionen was obtained.

Example 5

100 files methyl ester ion ni-xylenediamine diaceai. ^l '3.5 file C i Iy cerindiglycidy lather llpow equivalent:

1 39.5) and 200 parts of ethanol than 1 ösungsmittel w ere a Polyaddilionsreaktion in a Stickstoffstroni at a temperature between ⁷ O wna SO (during

Subjected for 2 hours with stirring. The saponification was carried out at a temperature between 50 and 100.degree with 245 files of a 10% aqueous hydrochloric acid solution stirred.

After the stranding had ended, 270 pieces of 10% aqueous sodium hydroxide solution were added to the reaction mixture. uiul water, methanol and methanol were distilled off. The resulting plastic was dried under reduced pressure. As described in Example 1, the plastic was further used. The plastic material obtained consisted of a white, hard and brittle powder with little water-solubility. The \ usbeute was 4 ^l) .4%. The nitrogen content was 4:55% (calculated 4. ^1M ",,).

The procedure from Example I was repeated, with the difference. that 3.0 g of a 15% wäl.lrigei> solution were eingesctzi to Kupier- UNOE ( "admiiimionen / u remove. S ⁷ .6""the Kupierionen and SV>the""(" were admiiimionen so einlernt.

Example 6

KM) Parts of Athy! Ester of N.N.N - (fnc.irbow-älhy lidiäthyientriamin. 52.6 Parts 1.3-Bis (1.2-tipo \ ypropowi-ben / ol and 150 parts of benzene were, as in Example ! described, / brought about a reaction. The product obtained was, as described in Example i, further cleaned. However, the saponification was carried out in such a way that 2 ^ 7.4 parts of a 10% aqueous Caustic soda were used. The yield was 74.5%. Kiii biaßgeibes soft. pul \ erföi iviigcs poIvmerisat has been received. The nitrogen content was 6.91% by weight (calculated 7.03%).

2.0g of a I ^s ",, aqueous solution of the resin \ iiirden used, as described in Example I to Kupfenonen [iwo lead ions. / W unregistering. 92.5"., The copper ions and konnlen ii '' 5.3 "i'iι Hlciiouen graze so far away

Example 7

70 parts of Mjthvlestet von N.N.V.N '-iTelra-carhowällivll-triälhvlcntetiamine and 2S.3 parts N.N -Bis- | 2.3-T.po \ v propvll-pipeiazin were a Polvaddi- " tion reaction with stirring in a nitrogen atmosphere at an I eniperalur between 90 and 100 (choosing 1.5 subject to Siiiniles. The saponification and the Cleaning of the plastic was carried out as described in Example 1. Tin pale yellow. hard. :, powdery polymer with good water solubility has been received. The yield was 79.4 "". The nitrogen content was 11.50 "" Ibeechnei II.66 "" i.

The procedure of Example I was repeated, with the difference that 1.2 g of a 15 '\, igen .ή aqueous solution of the plastic were used and 91.4 "ι · the copper ions and 92.0" ,, the ('ailmiumionen could be removed.

Example

50 parts Met Iniester von N- () ctvl-N "-carhoxvätlnläthv lendianiin. 31.S parts of AtIn lengkkoldiglveidvlather and 55 parts of toluene ethanol (I: II were a polvaddilioiisreaklion with stirring in a nitrogen stream subjected to a temperature between 75 and ι, SO C for 3 hours. The saponification and the cleaning of the plastic was carried out as described in Example I. The accruing Plastic was a white, hard powder with poor water solubility. The howl was ■, · 92.5 "ii. The nitrogen content was 6.39" ,, calculated ίοΓΊι).

50 parts of Metln lesler of N-Methv 1-N -carhowäihvläthvlenediamine. 51.2 "parts of Athvlenghkoldiglvcidvläther and 30 parts of toluene ethanol (1: 1) were n as Weiler described above, brought to reaction. ϊjus accruing roivmcnsai wai a weii.ies. iianes Powder with a low water solubility.

2.2 g of a 10% aqueous solution of a plastic, obtained from N-OcUl-N -carhoxväthvläthvlen-.: diarnine as starting material. w ic as in example I. described for the removal of copper ions. 97.5 ",, of the copper ions could be removed.

LS g of a 15 "igen aqueous solution of a plastic, obtained from metal ester of N'-Melh \ l- "., N -carboxv methvläthvlenediamine as a starting material. were used to remove copper ions and cadmium ions. S2.4% of the copper ions and N4.7% of the cadmium ions could thus graze away. -,

Example 9

IU) parts N- (2-H_vdrox \ octv I) -N-! propioniirilläthvlenediamine (whereby the 2-H \ droxvalkvlgruppe contained between 20 and 30 carbon monomers !. 157.4 « Parts of polypropylene glycol diglycidyl ether IF. pox ν equivalent: 190.0) and 100 parts of isopropanol underwent a polyaddition reaction in a stream of nitrogen at a temperature between SO and N5 C during

3 Sumden subjected The saponification was with * 75.3 parts of an aqueous 20% hydrochloric acid solution at a temperature between 50 and 100 ° C

4 hours ago. and the saponified product

was neutralized with a 5 "strength aqueous sodium hydroxide solution. The misehutii! was concentrated and reduced dried under reduced pressure. By tweaking \ iisf; Ilseii from an I) MT -, \ celon medium purified the product and obtained an acid type plastic. The P'oilukl thus obtained was a white one hygroscopic plastic. The yield was 50% and the nitrogen content was 4.23% 4.37 ",,). The plastic of the acid component was treated as described in Example 3, so that a plastic was received in Na -Torm. The plastic obtained was white and elastic and easily soluble in water.

3.0 g of a 15 "» strength aqueous solution of the plastic were used to remove copper, CailTiiumiiiid Lead ions are used as described in Example I. 99.2 "» of the copper ions. 99.4 "» of the cadniiiimioiien and 99. V '"(kr trillion could iMilfi-rnl wcnlrn

Example 10

(ο parts of huIv lesler of Athvleniliamindipropionäure and S2.6 parts Soibiuliglvcidvlälhcr (Epoxuläi | ui \ alent: 150) were subjected to a polarization reaction in a nitrogen stream at a temperature between 70 and 50 ° C for 1.5 hours and cooled to a temperature of 30 to 40 ° C . 2.S5 I rush Diäthvlentrianiin were added to the Reaktionsmiscliung. NO "» of the resulting mixture were / v. a processed Tiim. the remaining 20 "ι the mixture was diluted with toluene and Volumanteilen 20 in a thin layer on a vorhehandeltes Gewehe from a polyamide of hexamethylenediamine and adipic acid. The TiIm around the tissue was heated for 7 hours to a temperature between 130 and 150 C to harden the plastic. The hardened TiIm was colorless, crystal clear, elastic and brittle, so that it was easily could be crushed to a particle size between 0.31 and 0.127 mm. The polyamide fabric covered with the mixture was white and less flexible. The finely crushed plastic uiiii lias mn iiei mixture üiiei / ogene roi \ aiiiiiigewehe were in an aqueous Ι0% ϊ ^ .. · ί sodium hydroxide solution at a temperature between XO and 100 ° C

, saponified for 2 hours. The products were washed with distilled water and under reduced pressure Print dried. The finely divided plastic and the polyvinyl chloride fabric coated with the mixture were white, hard and insoluble in water.

The degree of curing on finely divided plastic was 91.4 "ti. After saponification, an experiment was carried out with the plastic with a grain size between 0.31 and 0.12 mm to determine the exchange capacity for copper, cadmium, lead and mercury. The capacity was 30.5 g / kg -R for Cir '. 54.lgkg-R for Cd ² ". 96.7 "g / kg-R for Pb ^; " and 120.0 g kg-R for mercury ions. To determine the exchange capacity, 1.0 g of the cured plastic was added to one liter of an aqueous one

, I ösiintz the given I contained and the ζ "υnlcrs ^1! Chendcn MeUiihonen. For copper, the solution of copper sulphate was, for cadmium from cadmium sulfate. Of lead from lead nitrate and mercury from mercuric chloride. The various mixtures were

~:! ap.iisiim hot room temperature 3 hours! "! left to stand for ¹ and 20 hours, after which they were filtered. The content of 1ppml of copper, cadmium, lead and mercury ions in the filtrate was

uhsorptionsspektriimanalyse determined and so the exchange Maintain capacities.

Example 11

K) O parts of m-XyI.iIdiamine-12-methyl-propionitrile). IS IS parts 2.2-bis- (p-1.2-epo \. \ Propo \ y phenyl! -Propane and 150 parts of benzene were subjected to a polyaddition reaction with stirring in a stream of nitrogen at a temperature between 70 and 50 ° C. for 4 hours, on a Cooled to a temperature of 30 to 40 ° C., mixed with 4.6 parts of ethylenediamine and processed into a film. With removal of the benzene, the film was cured at a temperature between M) O and 120 ° C. for about 10 hours. The product was a clear, hard, slightly compliant, cured, pale yellow film. The hip of the cured film was; 'u a particle size between 1.27 and 0.21 microns. crushed and saponified in an aqueous 10% sodium hydroxide solution at a temperature between 70 and - "100 ° C for 4 hours. The remaining half of the film was saponified in the same way, but in the form of a deep film The hardened plastics were filtered off, washed first with water, then with acetone and dried under reduced pressure. Pale gel. Hard, resilient plastics that were insoluble in water and in organic solvents were obtained. The yield was ¹ %. The (icsamlauxiaiischkapa / ät in be / ug on Cu'- and "(d ^: 'ions, determined (by the method described in Example 10, with the Iiterschicd. That a cured plastic with a grain size between 0.41 and 0.21 mm / t was 32. ') g kg-R for copper ions and 60.2 g kg-R for cadniium ions

Example 12

100 parts of poly-12-methylethylethyleneimine). ¹ M portions of methacrylonitrile and 100 parts of ethanol toluene 11: 1), '' subjected to between 70 and HO C for 6 hours, to a temperature around 40 C "a Ailditionsreaktion at a temperature ■ cooled and mixed with 41.6 parts of Viny lev ciohexend IOx yd I Epoxy equivalent: 70 III mixed. The mixture was subjected to a polyaddition reaction in a Sticksloffstrom at a temperature n / wipe XO and ^l) 0 ( 'during IO subjected hours, cooled iil'eine a temperature / wipe 30 and 40 C, mixed with 2.1 parts Diäthvlentrianun and / i ¹ a film The film was cured at a temperature between> 150 and 1X0 C for 20 hours, with ethanol and toluene removed from the lines. u wipe mm milled a Parlikelgröße / 00:41 and 00:12. ">. The finely divided resin was in an aqueous 20" iiitiLMi Sal / hei säiirelösimg a temperature / wipe XO and 100 (twisted for 3 hours. The mixture was hone 30 ¹ J a 2 () "nigen Niilronkiiigx mul / l and hot a teinpenitiir / ui ·«> see 60 and 7 (1 (stirred for one hour. D; is l'riijiikl was aillillriert. washed with water and then with milk i \\ n \ under veruiiiiderl em pressure gel rock ncl. Lin Ma ßgelbcr hardened kiinsi- ■. | O | f. which is insoluble in most of the organic dissolving media ><'< . winds resound The \ uxtoday any ^C ) X '\, The lotale \ iislauschkapa / iläl in relation to („) ueek silhei- and kuplerioncn. Diin.li determines the method described in Example IO with a plastic grain size between 0.41 and 0.21 mm. betruji 205.5 g / kg-R for mercury and 63.2 g / kg-R for copper ions.

Example 13

100 parts of Polv (2-dimethylethylamineimine |. 126.1 parts Butyl acrylate and HK) parts of ethanol underwent a Michael addition reaction at a temperature between Subjected to 70 and 80 C for 8 hours and cooled to a temperature of 40 C. the 88.3 parts by weight of 1,4-bis (1,2-epoxypropoxy) benzene were added to the reaction mixture, and a mixture was added Polvaddilion reaction in a nitrogen stream at a temperature between 70 and 80 C during

Subjected for 3 hours, cooled to a temperature between 30 and 40 C and treated with 10 parts of triethylene ! etramin versetz! The mixture was made into an IiIm, removing the ethanol. Of the LiIm was cured at a temperature between 120 and 130 C for 10 hours. A clear one colorless, slightly more flexible, more resistant, more hardened Film was received. The cured film was in an aqueous 10% sodium hydroxide solution at a temperature between XO and KK) C "during

Saponified for 4 hours. After saponification, the film was washed with water and dried, so that ¹ ci; i white, hard, hardened plastic that was insoluble in water and in organic solvents. was obtained. The howl was X4.6 "" The total Ausiaiischkapa / ät Rir copper and (,) uecksillv; rionen. Determined by the method described in Example 10 with a hardened plastic with a grain size / between 0.41 and 0.21 mm was 261 g kg- R for mercury ions around X 1.6 ü ksi-R for copper ions.

Example 14

50 parts of ethyl ethylenimine. 42.4 parts of methyl crolonate and 100 parts of toluene ethanol H: II were subjected to an addition reaction at a temperature between 70 and XO C for X hours and aiii a temperature of 40 C was cooled. The reaction * mixture was mixed with Xl.0 files 2.2-Bix- (pl.2-Fpo \\ - propoxyphcnyl-propane and subjected to a poly addition reaction in a stream of nitrogen at a temperature between 70 and 80 ° C. for 2.5 hours. The reaction solution was cooled to a temperature of 30 to 40 ° C., 5 parts of dihydric triamine were added and a film was processed, removing loluene, ethanol and similar solvents. The film was heated to a temperature between 120 and 130 ° C C choosing 6 sense the ausgchärlel. the resulting resin was clear pale yellow, hard and brüchig.so that it easily / u Einei grain size / wipe described 0:41 and 0:21 mm could be processed. as in example 10, wiirdi the saponified plastic, so that a Pale yellow, hard and slightly brittle plastic, which was obtained insoluble in water and in most organic solvents. The howling was 43.5%. The total exchange rate in relation to copper R and mercury ions, determine ¹ according to the procedure described in Example 10, with the hardened polyeneiisal grain sizes between 0.41 and 0.21 mm. helniü ¹ X ⁷ ? - kg-R Iu Qiiet. ksilhci ionen and 'MJ << _ ki'-K liii kupl'ei ionen

Example 15

100 parts of methyl ester of ethylenediamine dipropionic acid, 240.3 parts of 2,2-bis- (pl, 2-epoxypropoxyphenyl) -propane and 100 parts of toluene were subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 80 and 90 ° C. for 4 hours a temperature between 30 and 40 ° C. The reaction mixture was admixed with 2.1 parts of diethylenetriamine as a curing agent. The mixture was slowly poured into 2000 parts of an aqueous 0.5% polyvinyl alcohol solution (degree of polymerization 1000 to 1500) so that a suspension in This suspension was kept at a temperature between 80 and 180 ^° C. for 5 hours, toluene being distilled off and white spherical particles of a hard, resilient, resilient, cured plastic being obtained. The plastic was washed with hot water to remove polyvinyl alcohol, and with 1.2 parts of a 5% aqueous sodium hydroxide solution at egg saponified at a temperature between 90 and 100 ° C. for 3 hours. After the saponification, the product was washed with distilled water and dried under reduced pressure, so that white spherical particles (0.41 to 0.21 mm) of a hard and slightly flexible, cured marriage-forming plastic were obtained. The yield was 94.S ¹ O.

The total exchange capacity with respect to mercury and copper ions, determined by the in Method described in Example 10 with spherical particles of the cured polymer of one grain size / between 0.41 and 0.21 mm was 181 g kg-R for mercury and 58.4 g kg-R for copper ions.

B e i s ρ i e I 16

KK) TeUe Melhylestei "from Ethylcndiamindipropionat. 197 parts of Polsalhyleiiglykoldiglveidyläther (Lpoxyequivalcnt: 170.0) and 200 parts of toluene were a polyaddilion reaction in a stream of nitrogen at a temperature between 50 and 85 ° C Subjected for 3 hours, cooled to a temperature between 30 and 40 C and rush with 2.1 '!' Dietary triamine as I lärtunysniitlel versel / t. the Curing and saponification were as in Example 15 described, performed, with the difference that 2500 parts of an aqueous polyethylene lauryl ether solution (Molar number of ethylene oxide added: 10 minor instead of the polysinyl alcohol for hardening used winches. The impacting plastic was a white, soft product in the form of weak spherical particles that were insoluble in water and organic solvents. the Howling was K5 "". The total listening capacity in relation to Quei-k-ilberions. determined by that in example Kl bes \ h; < henc process with spherical pins of the hardened plastic son 0.41 to ΙΙ..Ί well. beiiiiL '274 g kg-R.

Example 17

Mi I i-iL \ IeI hs read ei \ on m - \ s I old ia in ι nd! Acetic acid. "■ Λ Ich- i. 1-Hh-l 1.2-I powpropow (benzene and ■ ι 'Ι · ι!. · Lienzo! Were a Polsaddilionsrcaklion ■■ UiKiI' NiicksUilMroin at a temperature between .. li.-ii '·> Iiiul M) (during ⁽ hours subject. .Iü! E;: v I.-Ii-.pei .HUi / wischen ^ M and 40 (abkiihli iiiiil inr MI rush I> u Ills lent n.imin, ils I left

medium offset. The curing and saponification were carried out as described in Example 15, with the Difference that 1000 parts of an aqueous 0.5% polyethylene glycol solution (molecular weight = 2000),

% were used for curing. The resulting hard and flexible plastic was in the form of white spherical particles that were insoluble in water and in most organic solvents. The yield was 86%. The total exchange capacity

The rate in relation to Cu ⁺ ions, determined by the method described in Example 10 with spherical particles of the cured polymer with a grain size between 0.41 and 0.21 mm, was 36 g / kg-R.

,. Example 18

50 parts of methyl ester of m-xylenediamine dinropionic acid, 43.3 parts of propylene glycol diglyudyl ether (Epoxy equivalent: 104.6) and 20 parts of benzene a polyaddition reaction in a stream of nitrogen

Λ; at a temperature / wipe 70 and 80 Γ during Subjected for 2 hours, cooled to a temperature between 30 and 40 C and treated with 1.1 parts of diethylenetriamine offset. The following reactions were carried out as described in Example 15 with

> -> the difference that 900 parts of an aqueous 1% Polyvinylpyrrolidone solution (molecular weight

= 10,000) were used for curing. White, spherical particles, (0.21 to 0.07 mm) one hard and brittle plastic that is immersed in water

κι and in most organic solvents was insoluble. were received. The yield was 76 "ii. The total exchange capacity based on Cir '. determined by that described in Example 10 Process with spherical particles of the hardened

η plastic with a grain size / between 0.21 and 0.12 mm. was 76.4 g kg-R.

Example 19

KK) Feile Pentaäthylenhexamin and 222 parts Mein (hylacrylat were a Michael addition reaction at a temperature between 70 and 80 (. 'for 5 hours subjected to a temperature around 40 C " cooled, with 106 parts of 1.3-bis (1.2-Hpoxypropoxy) -benzene and 3 (K) parts of toluene are added and one ■ r> Polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 C during Subjected to 4 hours. The reaction mixture was cooled to a temperature between 30 and 40.degree and with 2.1 parts of ethylenediamine as rlärtungsmitlel mi versetz '.. The hardening and the saponification were as described in Example 15, with the difference that 3500 parts of a 0.5 "igen aqueous carboxymethyl cellulose solution for curing were used. Pale yellow spherical par-vi likel of a hard one and very resistant to shock Plastic that was insoluble in water and in most organic solvents. w lines echo. The howl was 84%. the lolale Aiislauschkapazitiil in relation to C'ir '.determined mi by the procedure described in Example K) mil spherical particles of the cured polymer a grain size between 0.11 11 πι Ι 0.21 mm. was 42.4 g kg-R. l-'iir Mercury ioneii was the \ iisiauschkapaziliit 27X g kg-R.

Example . ¹ I)

'I) I hurry Pols -12-ällis latin leniniinl. H.I I hurry \ erslinliil and 50 parts of ΛΐΙι.ιηοΙ were one \ ddilioiis-

reaction at a temperature between 70 and 80 C for 10 hours, cooled to a temperature of 40 C and treated with (7.9 parts 1,4-bis (1,2-epoxypropoxy) benzene and 50 parts toluene. The mixture was subjected to a polyaddition reaction in a stream of nitrogen for 4 hours at a temperature between 70 ° and 80 ° C. Curing and saponification were carried out as described in Example 15. Pale yellow spherical particles (0.635 to 0.15 mm) of a hard iu and strong , to shock-resistant plastic, which was insoluble in water and in organic solvents, was obtained. the yield was 73%. the total Austauschkapazilät with respect to Cir ⁺ as determined by the beschriebcne in example K) method with spherical particles of the cured resin of a Grain size between 0.4! and 0.21 mm. was 72.4 g / kg-r.

ο ..;. ";., ι 11

IJ \ - I Λ J »I V. I _ I

100 parts of poly - (ice - 2.3 - dimethyläthylenimii'l. 94.7 parts of Melhylaerylat and 200 parts of toluene ethanol (1: 1) underwent a Michael addition reaction at a temperature / between 70 and XO C for 2> Subjected to X hours. The renction mixture was cooled to a temperature of 40 ° C. and treated with 158.1 parts by weight of 2.2-bis (p-1.2-epoxypropoxyph> nyI! -propane verset / l and a polyaddition reaction in a nitrogen atom at a temperature between see subjected to 70 and 80 C for 3 hours. The reaction mixture was added by weight Dietary triamine versel / t. The hardening and saponification were as described in Example 15 carried out. Pale yellow spherical particles 10.63 to r. 0.21 mm) of a hard one that is very resistant to shock Plastic that was insoluble in water and organic solvents. became echo. The yield was 76%. The total eligibility in be / ug on copper and Quecl. silver ion. determined by the method described in Example 10 with spherical particles dis cured polymer with a grain size / w see 0.63 and 0.41 mm. was 251 g.'kg-R for Qiieksilberionen and 96.5 g / kg-R for copper ions. <">

Example 22

100 parts of polyethyleneimine. 140 IcMe metal acrylic and 150 parts toluene ethanol II: II were subjected to a Michacl addition reaction at a temperature between 70 and XO C for 3 hours and cooled to a temperature around 40 C. The reaction mixture was mixed with 74.0 parts of 1.3-bis- (1.2-Lpo \ vpropo \ y) ben / ol and a PoIn- ~ r> addition reaction in a slurry stream at a temperature of 70 and XO ( . 'subjected to curing for 3 hours and the hydrolysis were made as described in example 15, carried out with (.lern ^I:. nlei'sehie (l DALI MK) O parts of a 0.5 "" ϊμοη uiiHriue'i mi polyo \ yäthylennon> lphenollösuni! I \ ddukl in I IO MnI ^: \ th \ leno \ ydl. The Kuiistsioff was in l-'orni hlaßgelher, hard, spherical particles, which are insoluble in water and in most organic solvents "aivn. The \ u- · - r, ·, howl at rug X2 "n. The loiale \ iisiaiischkapa / iläl n be / iiu aiii (^ uecksilherionen. espiiniml by the method described in Example 10 with kiiüclföi mine ι particles of the hardened polymer a grain size between 0.41 and 0.21 mm, was 29] g / kg-R.

Example 23

100 parts of a copolymer of ethyleneimine and N-cyanomethyläthylenimiii (MoI ratio: 1.9), 21.8 parts of 2,2-bis (p-1,2-epoxypropoxypheny!) Propane and 120 parts of toluene underwent a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 80 C for 3 hours. The resulting polymerization solution was slowly, while stirring, in 1000 parts of an aqueous 0.5% polyvinyl alcohol solution (degree of polymerisation 1000-1500) which has been preheated to 70.degree was dropped. This slurried the plastic in the aqueous system. The floured one Plastic was then further heated to XX to 100 C for 5 hours, with toluene was distilled off. Yellow, spherical particles of a hard, resilient, elastic, hardened Plastics were obtained. The plastic was carefully washed with warm water to remove polyvinyl chloride / u remove. The plastic was in 1000 parts of a 5% strength aqueous sodium hydroxide solution 90 to 100 C for 3 hours saponified. The saponified plastic was made with distilled water washed and dried under reduced pressure. I-lin spl ary, hard, elastic, yellow, hardened Plastic (grain size 0.41 to 0.12 mm) was made so echo. . Yield X9. (I%. The total exchange capacity With regard to mercury ions, the spherical cured was as described in Example 10 Plastic with a grain size of between 0.41 and 0.21 is now determined. Tune capacity of 274 g kg-R was measured.

Example 24

2 (X) parts of a mixed poly nieri .ate of A lines in the in and the methyl ester of N-Alhyleneglycine IMoI ratio of 0.5: 9.5 |. 26.2 parts of Penlaery llirit diglycidyl ether and 220 parts of toluene were subjected to a polyaddition reaction in a slurry solution at a temperature of 70 and XO ('for 2 hours. The hardening and saponification of the plastic obtained were as in Example 2} described, carried out, with the difference that 1,500 parts of a 0.5 ″ igen polyvinylpyrrolidone solution instead of polyvinyl alcohol was used. The plastic obtained was hard, elastic and had a pale yellow color The form of spherical particles, which were hardly soluble in water and in most organic solvents, was found.

The yield was 87.4%. 100 ml of the plastic with a grain size of 1.27 and 0.31 in the luminosity hall 63.4%) were placed on a column on which ration I (Kl ppm belrug. brought nn urden (the total \ iistaiischkap.i- / iläl in lie / ug on copper ions hot Ι \ ίιυΙ-Κι 150 ml 2n sal / säiire were hot ^ n * 2 / \\ dem KiMislslnll. An den ¹ the Kuplei ionen .ulsoi bierl NNKi den N \ aren. «Jeueben. 7P.5" ,, ι! Ι.τ Kiiplenoneii could become sk NNowNewNs. The InIaIe \ iislaiisschkap.i- / ilät in he / in: on (. (necksilheimneii winde, nnic in

Example IO described, determined. It was 267 g / kg-R.

Example 25

230 parts of a copolymer of ethylene imine and the butyl ester of N-ethylene glycine (molar ratio 1: 9), 26.8 parts of polyethylene glycol diglycidyl ether and 240 parts of toluene were subjected to a polyaddition reaction in a stream of nitrogen at a temperature between 80 and 85 ° C for 4 hours subject. The following reactions were as described in Example 23, carried out with the The difference is that 2CO0 parts of a 0.8% strength aqueous carboxymethyl cellulose solution for curing were used. The plastic so produced was soft, brittle, yellow and was in the form of spherical particles obtained that were insoluble in water and in organic solvents. the The yield was 78.7 "... The total exchange capacity, determined as described in Example 10 with a spherical hardened plastic a ': r grain size between 0.41 and 0.21 mm. was 67.4 g kg-R for copper ions and 224 g kg-R for mercury ions.

Example 26

100 parts of a copolymer of ethylenimine and the methyl ester of N-carboxyüthylälhylenimin (Molar ratio 2: 1) were a polyaddition reaction in a stream of nitrogen at a temperature between 70 and 50 ° C. for 4 hours subject. The reaction mixture was cooled to 30 to 40 C, and 3 parts of diethylenetriamine as Hardening agents were added. The polymer obtained was stirred into 1000 parts of a aqueous 0.2% polyethylene glycol solution (Durchsehniltsmolekulargcwicnt 6CK) O) was added dropwise. As a result, the plastic was suspended in the aqueous star. The slurried plastic was heated to SS to 100 ° C. for 5 hours, during which time Toluene was distilled off. A hardened pale yellow, hard, more resistant and elastic Plastic was obtained. The product obtained was washed with warm water to remove polyethylene glycol to remove. The saponification was carried out in H) (K) parts of an aqueous 5% strength sodium hydroxide solution carried out at 90 to 100 C for 3 hours. After the saponification, the plastic was washed with distilled water and under reduced pressure Print dried, tin more spherical, harder, more elastic and pale yellow marriage-forming plastic (grain size 0.41 to 0.1 2 mm) was obtained. The yield was 81.4%.

With the spherical, hardened plastic a grain size / between 0.41 and 0.21 mm was determines the total exchange capacity. With respect to copper ions, a capacity of 72.4 g kg-R and with regard to silver ophthalmic a capacity of 27S g kg-R.

Example 27

The cured films and the polyamide fabric coated with the polymer solution of the by - ■ -. games IO and 11 were made with a vibrating electrometer subjected to determine the surface resistivity. The specific surface resistance of the coated polyamide fabric

2.3 χ 10 ⁸ U and that of the cured films in 4.4 χ 10 ⁷ U at a voltage of 1000 V and a test time of 4 seconds.

The coated polyamide, which according to Example 10 was obtained in an aqueous copper sulfate solution Immersed for 3 hours. It was then washed with water and under reduced pressure dried. The surface of the polyamide fabric on which the copper ions were adsorbed had a surface resistivity of

8.4 χ 10 ^h <>.

² "example

An aqueous 5 "solution was water-soluble Polymer from Example 1 was applied with a brush to a metal plate and at a

j-, temperature of 50 C during 12 suinds below ve. ; dried to a minimum pressure, so that a thin, clear film was obtained on the metal plate. This plastic-coated metal plate was kept in a room for 6 months.

JIi keep it. After 6 months there was no rust formation can be found on the Melallplatte, which is proven was. that the plastics of the present invention work well as rust inhibitors. One Another plate with a plastic coating was

j "i after 6 months in water at a temperature of 50 C for one hour, and the coating film of the water-soluble plastic was completely detached from the surface of the metal plate.

65 parts of butyl ester of ethylenediamine propion

i'i acid and 82.6 parts of sorbitol diglycol ether (epoxy equivalent 150) underwent a polyaddition reaction. as described in Example 10, subjected to a Temperature between 30 and 40 C and cooled with 2.85 parts of diethylenetriamine and 520 parts of toluene

π offset. The mixture was spread in thin layers a soft steel plate applied and at temperatures between 1 30 and I 50 C for 7 hours hardened. The coated plate had high corrosion resistance and was also against

vi Insensitive to rust formation, as specified below :

Coating film of the present invention

Alkali spray
(15 hours)

Salt water spray
(500 hours)

Checker test to determine the adhesion

no changes
detectable

no changes
detectable

90 100 or more

Claims (1)

Patent claims: 1. A process for the preparation of chclate-forming polymers, characterized in that poly-N-substituted polyamines obtained from polyamines of the formula R-NH (R ¹ NH) ₁₁ H, wherein R is hydrogen or an alkyl group having I to 8 carbon atoms or a / i -Hydroxyalkyl group with 2 to 8 carbon atoms, R 'is an ethylene, phenylene or xylylene group and π I or 2, or poly-N-substituted polyalkyleneimines, from polymers of Alhylcnimin, 2-Methyläthylenimine, 2-Ethy! Äthylenimin, 2, 2-dimethylethyleneimine, cis- or trans-2,3-dimethylethyleneimine or copolymers of ethyleneimine and N-substituted ethyleneimines obtained by substituting the active hydrogen atoms on the nitrogen atom of the polyamines or polyalkyleneimines with alkali metal salts or alkyl esters of a carboxyalkyl or a cyanoalkyl group, where the N substituent is a cyanoalkyl group of the general formula (CHR) _n CN, in which R 'denotes hydrogen or a methyl group and; i denotes I or 2 uten, or the alkali metal salt /. or the alkyl ester of a carboxyalkyl group of the general formula