CA1049195A - Polymers containing 8-hydroxyquinoline groups - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Homo- and copolymers of monomers obtained by acylation of 2-[4-hydroxy(or amino)phenyl]-2-[5-(8-hydroxyquinolyl)_7-propane with .alpha.,.beta.-monoolefinically unsaturated carboxylic acid halides or - anhydrides. As comonomers can be employed compounds containing one or more .alpha.,.beta.-olefinically unsaturated groups such as olefines, diolefines, acrylic acid derivatives, vinyl monomers. The polymers having molecular weights between 5000 - 500 000 can, be prepared by radical or ionic chain mechanisms, in continuous or discontinuous processes. They may be used for removing metal ions from their solution, for complexing of interferring metallic impurities in thermo-plastic or thermosetting resins or in form of their metal complexes as stabilizers for plastics.

Description

9~ 5 The invention relates to polymers which contain ~-hydroxyquinoline groups, and to the use of -these polymers as complex-~orming agents for metal ions and as stabilisers ~or plastics. Further uses will be apparent from the description.
It is known -to employ 8-hydroxyquinoline as a complex-~orming agent for metals in analy-tical chemis-try, since it forms inner complexes, so-called oxinates, which can be precipitated quantitatively, with numerous metal ions (compare R. Berg "Die analytische Verwendung von o-Oxychinolin ("Oxin~) und seiner Derivate~') t"The use of o-hydroxyquinoline ("oxine") and of its derivatives in analysis1'), 2nd edition, Stuttgart 1938 and R. Bock, Angew.
Chemie 67, 420 (1955)). In addition, 8-hydroxyquinoline exhibits powerful fungicidal and antiseptic effects. 8-Hydroxyquinoline is a compound which is readily soluble in customary solvents.
It is the object of the present invention to fix 8-hydroxyquinoline to organic macromolecules, whilst preserving the complex-forming action and the other properties characteristic of 8~hydroxyquinoline. Such products are intended to be used in industrial or commercial processes for removing and complexing me~al ion~
from solutions or, in a combination with metal ions, as stabilisers for plastics or, where appropriate, in plant protection or in antiseptic compositions~
The object has been achieved by alkylating 8-hydroxyquinoline with p-isopropenylphenols or p-isopropen~-anilines, and reacting the alkylation produc-t with a~-unsaturated carboxylic acids having 3-5 C-atoms or their derivatives,to give polymerisable monomers, Le A 15 2~1 - 2 -. ..
. , . ; ; . ~ ~ . .

~4g~95 and converting these polymerisable monomers into homopolymers or copolymers.
According to the invention there are provided polymers ~ ;
with average molecular weight of about 5,000 to 500,000, which comprise recurring polymerised units of a monomer o~ the formula I

C = C
R1 C = O

~ I

~ '.
OH
wherein X denotes -O- or -NH-;
R denotes H, -COOH or -COOR3 / with R3 = C1 - C1~ -- (linear or branched)-alkyl or cycloalkyl 7, R1 denotes H or CH3 and R2 denotes H or CH3 or contain these units in a copolymerized form.
Preferably, R and R1 denote H, R2 denotes H or CH3 and R denotes C1 - C8 alkyl or cyclohexyl.
The preferred average molecular weights are lO,OOO to lOO,OOO~
~n the present application, polymers are understood to include homopolymers and copolymers,and the end groups can be formed by the radicals of the initiators or regulators used in any particular case.

Le A 15 281 - 3 -9~9s The term copolymer comprises not only copolymers with a statistical distribution of the copolymerised mono-mers and block copolymers, bu-t also graft copolymers, where monomers are gra~ted onto a previously ~ormed homopolymer or copolymer. Statistical copolymers are preferred.
As comonomers, one or more monomers from the follow-ing groups can be employed for the copolymerisation with at least one monomer of the formula I:
a) a 9 ~-Monoolefines with 2-4 C atoms, such as ethylene, propylene, butene-l and isobutylene~
b) Con~ugated diolefines with 4-6 C atoms, such as butadiene3 isoprene, 2,3-dimethylbutadiene and 2-chlor~_ butadiene.
c) Acrylic acid and methacrylic acid, acrylonitrile and methacrylonitrile, acrylamide and methacrylamide, acrylic acid alkyl esters and methacrylic acid alkyl esters with 1-18, preferably 1-8 9 C atoms in the alcohol component, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the corresponding methacrylic acid alkyl esters.
d) Vinyl esters of organic monocarboxylic acids wherein the acid component contains 1-18, preferably 2-4 ~ atoms, such as vinyl acetate and vinyl propionate.
e) Monoolefinically unsaturated halogenohydrocarbons, preferably vinyl chloride or vinylidene chloride. -f) Vinylaromatics such as styrene, o- or p~methyl-styrene, a-methyls-tyrene, a-methyl-p-isopropyls-tyrene, a-methyl-m-isopropylstyrene~p-chlorostyrene, but preferably styrene.

:' . ., ~, ' .

~4~ S
In this category, the monomers which polymerise less readily, such as ~ -methylstyrene and m- and p- isopropyl-~-methylstyrene are preferably always employed as a mixture with at least one other of the copolymerisable monomers mentioned.
g) Monoesters of ~, ~monoolefinically unsaturated monocarboxylic acids, with 3-4 C atoms, and dihydric saturated aliphatic alcohols with 2-4 C atoms, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxy-butyl methacrylate, 2~hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
h) N-Methylol ethers of acrylamide and methacrylamide, of the general formula II
H2 f - co IN - CH2 - OR2 R Rl II

in which R represents hydrogen or methyl, Rl represents hydrogen, alkyl, aralkyl or aryl, and R2 represents alkyl or cycloalkyl of from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or cyclohexyl. ~-The N-methylol methyl ether of methacrylamide is preferred. The monomers of group h) are employed, and incorporated into the copolymer, in amounts of 1-20% by weight, based on the total monomers.

. . ', . : :.: : . .: ~ ,:
., ... ..
;' : -. . .,' :

~C~49~L95 i~ Diesters and monoesters of maleic acid, fumaric acid and itaconic acid with 1-18 C atoms in the alcohol component, and also maleic anhydride, maleic acid or ~umaric acid, amides of maleic acid and fumaric acid, maleimides and unsaturated copolymerisable polyes-ters whic~
contain the radicals of maleic acid and/or fumaric acid as polymerisable constituents.
~) Vinyl alkyl ethers with 1-4 C atoms in the alkyl group, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and vinyl butyl ether.
k) Monomers which have a crosslinking action and contain several non-conjugated olefinically unsatura-ted carbon-carbon bonds, such as divinylbenzene, diallyl phthalate, divinyl adipate, acrylic acid allyl ester and/or methacrylic acid allyl ester, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallyl cyanurate, triallyl isocyanurate, triacryloyl-perhydro-S-triazine, bis-acrylates and bis-methacrylates of glycols or polyglycols with 2_20 C
atoms, such as ethylene glycol diacrylate or dimethacrylate, propylene glycol diacrylate or dimethacrylate 9 butylene glycol 174-diacrylate or 1,4-dimethacrylate, tetraethylene glycol diacrylate or dimethacrylate and t~s-acrylates and tris_ methacrylates of trimethylolpropane and glycerol.
The crosslinking monomers of group k) are preferably employed for the copolymerisation in amounts of 0~1-12% by weight, based on total monomers. They are incorporated in~to the copolymer in the same amountsO
In addition, primary, secondary or tertiary amino-alkyl esters of acrylic acid or methacrylic acid with, preferably, 2-4 C atoms in the alkyl group, and glycidol Le A 15 281 - 6 --~9~5 acrylate or methacryla~e, can also be employed as comonomers and can, if desired, be crosslinked, during or af-ter the copolymerisation, via the amino or epoxide group, respectively.
Preferably, comonomers of groups c) and f) in combina-tion with cornonomers of group k) are employed for the copoly-merisation.
The comonomers can - unless stated otherwise - be employed for the copolymerisation in amounts of 5 to 95% by weight, pre~erably 50 to 90% by weight, based on total mono-mers. Correspondingly~ the monomers of the formula I
account for 5 - 95% by weight, preferably 50 to 10% by weight. -They are also preferentially incorporated into the copolymers in these proportions. If, in addition to the customary co_ monomers, comonomers of groups h) and k), or ye-t other mQno-mers copolymerisable with the monomers of the formula I) are also employed) their proportion shown under h) and k) is con-tained in the total proportion of the comonomers (5-95% by weight).
The homopolymers and copolymers can be prepared by radical or ionic chain mechanisms, in continuous o~ discon-tinuous processes.
In the case of the ionic polymerisation, catalysts of the anionic reaction type are preferably employed9 in amoun-ts o~ 0.01-5% by weight, preferably 0.01-2% by weight, based on total monomers; examples are metal alkyls, alkali metal alcoholates, metal amides or metal hydroxides9such as but~l-lithium, zinc alkyl with 1 - 4 C atoms in the alkyl groups, lithium alcoholate, potassium tert.-butylate, sodium amide or mixed catalysts,such as aluminium triethyl/titanium-Iv chlo-ride, used in aprotic solvents,such as9 for example, dimethyl-Le _ 15 281 - 7 -. ",' ' : ~, . :

~491~S
formamide 9 dimethylaniline, benzene or toluene, at tempera-tures of about -80C to approx. +110C, preferably at -60C
to ~10C~ if appropriate under pressure.
Preferably, the polymerisation -takes place in accord-ance with -the radical chain mechanism, in -the presence of subs-tances which yield free radicals.
Suitable substances of this type are inorganic per-compounds, such as potassium persulphate or ammonium persul-phate, hydrogen peroxide, alkali percarbonates, organic per-oxide compounds, such as acyl peroxides, for example diben-zoyl peroxide, dichlorobenzoyl peroxide, di-tert.-butyl per-oxide and dicumyl peroxide, a~yl ~ydroperoxides, such as tert.
butyl hydroperoxide, cumyl hydroperoxide and p-menthane hydroper~
oxide, organic percarbonates such as cyclohexyl peroxydicar-bonate~ diisopropyl peroxydicarbonate and ethylhexyl peroxy-dicarbonate, and also tert.-butyl peroctoate, -tert.-butyl perpivalate and azodiisobutyronitrile. It is also possible to employ inorganic or organic per-compounds in combination with reducing agents, in a manner which is in itself known.
Examples of suitable reducing agents are sodium pyrosulphite or sodium bisulphite, sulphinates, iron-II salts, cobalt naphthenate, ascorbic acid and aromatic amines such as p-toluidine.
Metal complexes~such as acetylacetonates of mangan-ese and cobalt, and diacyl peroxide/tert. amine systems, are also suitable. However, the polymerisation can also be initiated by elevated -tempera-tures, light rays and high energy rays.
Preferably, the copolymerisation is carried out wi-th radical-forming substances such as azodiisobutyronitrile, Le A 15 281 - 8 -~; . . .

.,: .

:

1~49~g~
benzoyl peroxide or potassium persulphate/sodium sulphi-tec The amoun-t of catalyst which can be used lies within -the limi-ts usually involved, that is to say approximately be-tween 0.01 and 5% by weight, preferably be-tween 0.~1 and

2% by weigh-t, calcula-ted rela-tive to the total monomers employed.
The polymerisation can be carried out at temperatures of -20 to 160C, pre~erably at 60 to 110C, if appropriate under pressure, in accordance with the customary methods of bulk polymerisation, solution polymerisation, precipi-tation polymerisation, dispersion polymerisation, emulsion polymer-isation or bead polymerisation. Dispersion polymerisation and bead polymerisation, which - after separation from the dispersing medium - give the polymers in a form where they are immediately ready to use, are preferred. Solution poly-merisation is particularly preferred.
If polymerisation is carried out in solution, the customary solvents are employed. Alcohols, such as ethanol to n-butanol, iso-butanol and tert.-butanol, halogenated hydrocarbons such as methylene chloride, trichloroethyl~ne and tetrachloroethane, ketones such as acetone and ~ethyl ethyl ketone, esters such as ethyl acetate to octyl acetate, ethylglycolacebate and me-thylglycol acetate7 e-thylene glycol mono-methyl or bis-methyl ether, diethylene glycol mono-methyl or bis-methyl ether and aromatic hydrocarbons suc~ as toluene, benzene, xylene, dichlorobenzene and trichloroben-zene. The high polymers can be isolated either by steam~
stripping or by precipitation in a non-solvent such as pe-troleum, benzines, petroleum e-ther or methanol. They can also be isolated on screw avaporators. Further, -the Le ~ 15 281 _ 9 _ .' ' ' : ' , , ' ^

9~5 solutions can be isolated by spray-drying or drying in a thin layer evaporator, tubeevaporator or falling film evaporator.
The precipi-tation polymerisation is pre~erably car-ried ou-t in a good solven-t for the monomer in which, how-ever, the polymer is insoluble, such as, for example, in me-thanol or fluorochlorohydrocarbons, such as dichlorofluo-rome-thane.
The dispersion polymerisation or bead polymerisation is carried out in an aqueous liquor in the presence of the customary protective colloids such as methylcellulose, gelatine, saponified polyvinyl acetate, styrene-mal$ic anhy-dride polymers, precipi-tated calcium phosphate or aluminium hydroxy gels. In addition, buffer substances such as sodium carbonate, prim-, sec- or tert-sodium phospha-te and alkali metal bora-tes can be added. In order to control the par-ticle diameter, extraneous salts such as sodium sulphate, or alcohols such as butanol, can be present in amounts of 0.~ to 2% by weight, based on monomers~
The particle diameter can also be regulated by co-use of surface-active substances,such as fatty alcohol sul-phonates or polyethylene oxides in which phenols were used as the starter (reaction products of phenols with ethylene oxide) and the like.
It is importan-t to adjust the average molecular weight, and this can be done with the aid of 0~1 to 2% by weight, relative to total monomers, of a chain trarsfer agent.
These agents are mercaptans, such as tert.-dodecylmetcaptan9 xanthates9 thioglyceroly nitrotoluenes, cumene9 halogen derivatives such as carbon tetrachloride, haloforms such as Le A 15 281 - 10 -:~Lai 49~9S .
chloroform, methyl vinyl carbinol, allyl alcohol and the like. The regula-tors are employed in such amounts that average molecular weights of 5,000 -to 500,000 result.
~:Eter -the dispersion polymerisation or bead polymerisation the particles of diame-ter 10 ~ to 2 mm are separated from the aqueous liquor and washed and dried. Thereafter they are, in most cases, in a free-flowing form.
The polymers, carrying 8-hydroxyquinoline groups, can be used, in the solid form or dissolved in organic solvents, for removing metal ions of the transition elements of the periodic system of the elements, that is to say of the ele-ments Sc to Zn (atomic number 21 to 30), Y to Cd (atomic numbers 39-48), La to Hg (atomic numbers 57-80), Ac to U
(atomic numbers 89-92) and of magnesium, calcium, aluminium9 lead, tin and bismuth, from solutions.
To improve the absorptive capacity of the particles 7 the latter can be swollen before use, for example wi-th xylene or toluene. The absorption of the metal ions is reversible.
The metal ions can again be removed by elution with strong acids or bases or stronger complex-forminK agents such as acetylacetonates and complexones such as nitrilotriacetic acid. me polymers described are therefore of particular interest for the removal of traces of heavy metals from industrial effluents or process sewage.
The polymers according to the invention can also be employed for the complexing of interfering metallic i~puri-ties in thermoplastics or thermosetting resins, in amoun~s of 0.01 to 10% by weight, based on the total mixture. Thus, as is known, iron impurities in polyvinyl chloride lower the heat s-tability,but the latter can be improved by complexing Le A 15 281 - 11 -:. ' , . ~' . ..

1~49~L95 wi-th the polymers described.
The polymers according to the inven-tion can also be used, in the form of -their metal complexes, for example with cadmium, tin or lead, as stabilisers for plastics. Such plastics are polyvinyl chloride or its copolymers,such as e-thylene/vinyl chloride or vinyl ace-tate/vinyl chloride co-polymers,or polyethylene, polypropylene,polYacrylates, co-polymers of acrylates or methacryla-tes and at least one fur-ther monomer, vinyl acetate polymers, ethylene/vinyl acetate copolymers, polycarbonates, polysulphones, polyphenylene oxides, styrene copolymers, polymers of the ABS type (acrylonitrile-butadiene-styrene graft polymer thermoplas-tics), polyamides of the nylon type or polycaprolactam, poly-ethylene terephthalates, polyacetals and the like. The heat stability, weathering resistance, stress crac~ing and sensitivity to hydrolysis can be improved, or influenced, by addition of the polymers according to the invention.
The percentages in the examples are by weight, unless sta-ted otherwise. The average molecular weigh-ts are always determined by membrane osmometry m e starting materials described below, and their manufac-ture9 do not form a subject of the present application.
Preparation of the starting material~ 2-[4-hvdroxy~henyll-2-[5-~8-hydrox~quinolyl)]-propane.
1,508 g of 8-hydroxyquinoline, 483 g of p-isopropenyl-phenol and 150 g of bentonite (acid catalyst K 20 from Messrs. S~dchemie, Munich) are brought -toge-ther and heated to 180C for 24 hours in a nitrogen atmosphere under reflux.
The reaction mixture is then fil-tered through a pressure fil-ter to separate off the solid catalyst.
After addition of methylene chloride/water, a part of the 2-[4-hydroxyphenyl~-2-[5-(8-hydroxyquinolyl)]-propane is Le A 15 281 - 12 -. . . . ..... . .

~6~4~L95 obtained in a crystalline form. The mixture which remains is subjected to a steam distillation, whereby -the 8-hydroxy-quinoline employed in excess can be recovered. On renewed addition of methylene chloride, a fur-ther part of -the functional hydroxyquinoline is ob-tained in a crystalline form.
The two crystalline fractions1 when combined, give a -to-tal yield o~ 460 g (46% of theory). After extraction with benzene in a Soxhlet, colourless crystals of melting point 139C are obtained from benzene.
Anal~sis:_ C H _ N
calculated 77.4% 6.10% 5.01%
found 77.5% 6.03% 4.87%
Preparation o~ the startin~ material: 2-~4-methacryloylox~-phen~ 2-[5-(8-hvdroxyquinolyl ~-propane 279 g of 2-[4-hydroxyphenyl]-2-[5-(8-hydroxyquino-lyl)]-propane are introduced into 1,120 ml of methylene chloride and a solution of 190.8 g of sodium carbonate in 1,000 ml of wa-ter together with 3.0 ml of triethylamine is added dropwise at 13C. 110 g of methacrylic acid chlo-ride and 200 ml of methylene chloride are then added over the course of 20 minutes.
The mixture is stirred for a further 20 minu~es and the organic phase is separated off and washed once with dil-ute HCl and -then with water un-til neutral. After concen-trating the organic phase in vacuo~ 180 g (52% of theory) o~
the methacrylic acid ester of 2-(4-methacryloyloxyphenyl)~2-[5-(8-hydroxyquinolyl)]-propane are ob-tained from ethanol as colourless crys-tals of melting point 141C, calculated 76,06% 6.09% 4.03%
found 75.6% 6,05% 3.94%
Le A 15 281 - 13 -.

Preparation of the starting material: 2-~4-am noph~yll-2-r 5-(8-hydroxyquinol~l )J -pro~ane 2,180 g of 8-hydroxyquinoline, 400 g of p-isopropen-ylaniline and 300 g of ben-tonite (acid ca-talys-t K 20 from Messrs. Sudchemie, Munich) are heated for 26 hours to 160C
under ref]ux in a nitrogen atmosphere. The reac-tion mix-ture is filtered through a pressure fil-ter and then succes-sively subjected first to a vacuum distillation and then to a s-team distillation. This results in almost quantita-tive recovery o~ the 8-hydroxyquinoline employed in excess.
Methylene chloride is then added to the reaction mixture and the organic phase is separated off. The residue remaining after concentrating the organic phase is extracted with a methylene chloride/petroleum ether mixture and 3~ g (46% of theory) of 2-(4-aminophenyl)-2-[5-(8-hydroxyquinolyl)~-pro-pane of melting point 105-107C are obtained. Crystal-lisation from ethanol raises the melting point of the colour-less crystals to 109C.
Analysis: C H N
.
calculated 77.7% 6.46%10.02%
found 77.5% 6.58%9.88%
Preparation of the startin~ material 2-[4-methacrylamido-phen~ll-2-[5-(8-hydrox~quinolyl)l-propane 200 g of 2-(4-aminophenyl)-2-[5-(8-hydroxyquinolyl)]-propane are dissolved in 200 ml of methylene chloride an~
500 ml of pyridine. 75.0 g of methacrylic acid chloride in 19000 ml of methylene chloride are slowly added dropwise ~o -this solution. The mixture is left to stand for 15 hours at room temperature and the solvents are -then removed in vacuo. The residue is taken up in methylene chloride ~nd washed twice with 1 N H2S04 and then with water. After Le A 15 281 - 14 -:

. . , .. . . . , . - .. .

:. , ~:349~9S
concentrating the organic phase, 205 g (80.5% of theory) of 2-(4-me-thacrylamidophenyl)-2-[5-(8-hydroxyquinolyl)~-propane are obtained in the form of colourless crys-tals of mçlting poin-t 126-127C from benzene/petroleum e-ther.
Anal~sis: C _ H N
calcula-ted 76.5% 6.30% 8.11%
found 76.3% 6.18% 8.02%

Homopol~merisation in toluene To a 50 per cent strength solution of 100 g of 2-[4-methacryloyloxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane in toluene and 1% by weight of tert. dodecylmercaptan, rela~ive to the monomer, are added dropwise 2% by weight of dibenzoyl peroxide, rela-tive to the monomer, disslv~ in~uene,atlOO~ over the course of 3 to L~ hours. Thereafter the mixture is stirred for a fur-ther 4 hours at 100C. The viny~ polymer is then either precipitated in me-thanol or poured out onto a metal sheet and dried in a vacuum drying cabinet. The average molecular weight Mn determined osmometrical~y was 19,500. Nitrogen analysis: calculated 4.03%~ found 3.92%.

~ .
To a 50 per cent strength solution of 20 g ilof 2-[4_ methacryloyloxyphenyl]-2-[5-(8-hydroxyquinolyl)]-proFane and 80 g of methyl methacrylate in toluene and 2% by wei~ht o~
tert dodecylmercaptan, relative to the monomer~ are added dropwise 2% by weight of dibenzoyl peroxide, relative to ~he monomers, in toluene, at 100C over the course of 3 to 4 hours. Thereaf-ter the mixture is stirred for a ~rther 4 hours at 100C. The vinyl polymer is then either precipi-tated in methanol or poured out onto a metal sheet and dried Le A 15 281 - 15 -: ' ,, ,. ' ' ; .' ' ' ,, . ' ~ ' ~' . : . . : ~ , ~ :, . .
:-. , .. . . : . . ~ . , , ~L~4~5 in a vacuum drying cabinet. The average molecular weight of t,he statistical copolymer was determined osmometrically~
Mn = 37,000, nitrogen analysis: calculated 0.8%, ~ound 0.78%.
Example 3:
Copol,,vmerisation wi-th styrene To a 50 per cent strength solution of 10 g of 2-~4-methacryloyloxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane and 90 g of styrene in benzene and 2% by weight of tert, dodecyl-mercaptan, relative to the monomers, are added dropwise 2%by weight of dibenzoyl peroxide, rela-tive to the monomers, in benzene, at 80C over the course of 3 to 4 hours. There-after the mixture is stirred for a further 4 hours at 80C.
The vinyl polymer is then either precipitated in methanol or poured out onto a metal sheet and dried in a vacuu~ drying ' cabinet. The average molecular weight of the statistical copolymer was determined osmometrically and was 42,000.
Nitrogen analysis: calculated 0.40%, found 0.38%.
Example 4:
Bead polymerisation 150 g of styrene, 12 g of divinylbenzene~ 2 g of dibenzoyl peroxide and 50 g of 2-[4-methacryloyloxy-phenyl-]-2C-5-(8-hydroxyquinolyl)]-propane are dispersed in 1,000 ml of water, 40 ml of toluene and 2 g of polyvinyl alcohol.
mis mixture,is heated to 80C for five hours with vigorous stirring and is then stirred for a further eight hours at 100C oil bath temperature and allowed -to cool slowly. The bead polymer is filtered off, washed with water and dried in a vacuum drying cabinet at 80C. The softening point o~
this crosslinked polymer is above 360C.
The product is crosslinked and practically insoluble Le A 15 281 - 16 -,. ~ ., . . ;
.. . .. .

~9~9~
in all solvents so that it was not possible to de-termine the molecular weight. Nitrogen analysis: calculated 0.95%, found 0.93%.
Example 5:
Terpolymerisation with stvrene and acryloni~trile 61.0 g of distilled styrene1 16.0 g of destabilised acrylonitrile and 23 g of 2-[4-methacryloyloxyphenyl]-2-[8-hydroxyquinolyl)]-propane are dissolved in chlorobenzene.
2 g of dibenzoyl peroxide in chlorobenzene are then added dropwise -to the reac-tion mixture over -the course of 3 hours at 100C. m e mixture is stirred for a further 4 hours and thereafter the polymer is precipitated in alcohol or the sol-vent is removed and the polymer dried in vacuo. The osmo-metrically de-termined molecular weight is 31,900. Nitrogen analysis: calculated: 6.37%, found: 6.29%.
Example 6:
90 g of styrene and 10.0 g of 2-[4-methacrylamido) phenyl]-2-[5-(8-hydroxyquinolyl)~-propane are dissolved in toluene together with 2% by weight of tert. dodecylmercaptan, relative to the monomers, and the solution is heated to 100C.
2 g of dibenzoyl peroxide in toluene are added dropwise over the course of 2 to 3 hours to this reaction mixture and the reaction is allowed to continue for a further 6 hours.
Thereafter, the product is either precipitated in alcohol Z5 or dried after removal of the solvent in a vacuum drying cabinet. The average molecular weight was determined osmometrically. Mn = 26,200. Nitrogen analysis: calcu_ lated: 0.81; found: 0.8%.
Example 7:
50 ml of 20% strength sodium hydroxide solution9 followed by 40 g of acrylic acid, are added to 10 g of 2-[L~-Le A 15 281 - 17 -:
. ~ , : . , : : ;

~L~49~9S

methacryloyloxyphenyl~-2-[5-(8-hydroxyquinolyl)~-propane in 150 ml of ethanol, whils-t stirring. 0.7 g of potassium peroxydisulphate as the ini-tiator is added and -the reaction mix-ture is heated to 70C. The reaction is allowed to con-tinue for a further 4 hours and is -then discontinued. The polymer which precipitates on cooling the reaction solution is filtered off and dried. The average molecular weight was determined osmometrically and is 5,900. Nitrogen analy-sis: calculated: 0.72; found: 0.68%.
Example 8:
5 g of -the polymer described in Example 2 in 6Q ml of methylene chloride are stirred with 0.85 g of mercury-(II~
acetate for 8 hours at room temperature. In the course thereof, a red colour develops. Analysis of the polymer:
10.2% of mercury.
me mother liquor contains 0.24 mg/l ^ 0.24 ppm of mercury.
Example 9:

3 g of the polymer described in Example 2 are dis-solved in 150 ml of methylene chloride and the solution is shaken with 180 ml of an 0.1% strength by weight mçrcury-II
acetate solution for 3 hours, m e phases are then separated and the mercury content of the aqueous phase is determined.
Residual content of Hg: 0.7 mg/l A 0.7 ppm of Hg~
Example 10:

4 g of the polymer described in Example 2 are dis-solved in 200 ml of methylene chloride and the solu-tion is shaken with 0.42 g of copper-~I acetate for 4 hours. The reaction solution is filtered and the residue which remains after removing the solvent is analysed. Copper content of the polymer: 2.9%.
Le A 15 281 - 18 - -~

,: .: . . . . .
~ ! , . ' ' . ' ~ ; ' ' ; ~ ' ~9~95 Example 11:
4 g of the polymer described in Example 7 are dis-solved in a water/ethanol solvent mixture and the solution is shaken wi-th 0.53 g of CuS04.5H20 for 2 hours. Af-ter filtra~
tion, the solven-t is removed and the residue which remains is examined for its copper conten-t. Copper con-tent of the polymer: 3.4%.
Example 12:
4 g of the polymer described in Example 2 are dis-solved in 100 ml of methylene chloride and -the solution is shaken with 81 ml of an 0.5% strength by weight nickel-II
acetate solution for 4 hours. After separating the phases, the organic phase is brought to dryness and analysed.
Nickel content of the polymer: 1.6%.
Example 13:
4 g of the polymer described in Example 2 are dis-solved in 200 ml of methylene chloride ard the solution is shaken with 1.01 g of lead-IV acetate for 4 hours. The solution is then filtered and concen-trated. The lead con-tent of the polymer was found to be 4.7%.

0.75 g of a vinyl polymer containing mercury, pre-pared analogously to Example 8 and having a mercury content of 3.1%, is dissolved in 30 ml of methylene chloride and the -solution is shaken with a solution of 0.3 g of potassium cyanide in 30 ml of water for 8 hours. The decolourisation of the polymer containing metal, which occurs during this treatment~ indicates re-complexing. The organic phasç is isolated and dried over sodium sulpha-te. It is then pre-cipitat~d in pe-troleum ether and the product is dried in vacuo at 80C~ Residual mercury conten-t in the polymer:
Le A 15 281 - 19 -9~L~5 0.3% of Hg.
Example 15:
2 g of a vinyl polymer containing lead, prepared analogously to Example 13 and having a lead content of 1.0%, are dissolved in 100 ml of methylene chloride and the solu-tion is shaken wi-th 50 ml of 0.1 N HN03 for 6 hours. ~he organic phase is then separated off, washed un-til neutral and dried over sodium sulphate. The solvent is stripped o~f and the residue is examined for its lead con-tent. Only traces of lead remained detectable in the polymer. Lead content of the polymer: Pb ' 0.05%.

Le A 15 281 - 20 -.

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A homopolymer or a copolymer of average molecular weights of about 5,000 to 500,000, which comprise recurring polymerized units of a monomer of the formula I

I

wherein X denotes O or NH;
R denotes H, -COOH or -COOR3, R1 denotes H or CH3, R2 denotes H or CH3 and R3 denotes C1-C18-(linear or branched)-alkyl or cycloalkyl and when present a comonomer selected from the group a) .alpha.,.beta.-Monoolefines with 2-4 C atoms, b) Conjugated diolefines with 4-6 C atoms, c) Acrylic acid and methacrylic acid, acrylonitrile and methacryloni-trile, acrylamide and methacrylamide, acrylic acid alkyl esters and meth-acrylic acid alkyl esters with 1-18, C atoms in the alcohol component, d) Vinyl esters of organic monocarboxylic acids wherein the acid component contains 1-18, C atoms, e) Monoolefinically unsaturated halogenohydrocarbons, f) Styrene, o- or p-methylstyrene, .alpha.-methylstyrene, .alpha.-methyl-p-iso-propylstyrene, .alpha.-methyl-m-isopropylstyrene or p-chlorostyrene, g) Monoesters of .alpha.,.beta.-monoolefinically unsaturated monocarboxylic acids, with 3-4 C atoms, and dihydric saturated aliphatic alcohols with 2-4 C atoms, h) N-Methylol ethers of acrylamide and methacrylamide, of the general formula II

II
in which R represents hydrogen or methyl, R1 represents hydrogen, alkyl, aralkyl or aryl, and R2 represents alkyl or cycloalkyl, of from 1 to 6 carbon atoms i) Maleic acid, maleic anhydride, fumaric acid, di or monoesters of maleic acid, fumaric acid, itaconic acid with 1-18 C atoms in the alcohol portion of the ester, amides of maleic and fumaric acids, maleimides and unsaturated copolymerizable polyesters which contain radicals of fumaric or maleic acid or mixtures thereof j) Vinyl alkyl ethers with 1-4 C atoms in the alkyl group, k) Divinylbenzene, diallyl phthalate, divinyl adipate, acrylic acid allyl ester and/or methacrylic acid allyl ester, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallyl cyanurate, triallyl isocyanurate, triacryloyl-perhydro-S-triazine, bis-acrylates and bis-methacrylates of glycols or polyglycols with 2-20 C atoms.

2. Polymers according to claim 1, characterized in that they consist of (A) 5-95% by weight of copolymerized units of monomers of the formula I and (B) 95-55% by weight of copolymerized units of at least one of the monomers styrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylic acid esters or methacrylic acid esters with 1-8 C atoms in the alcohol component, 2-hydroxyalkyl acrylates or methacrylates with 2-3 C atoms in the alkyl group, diesters and mono-esters of maleic acid, fumaric acid or itaconic acid with 1-18 C atoms in the alcohol component, vinyl alkyl ethers with 1-4 C atoms in the alkyl group, vinyl chloride, vinylidene chloride, vinyl esters of organic monocarboxylic acids with 2-4 C atoms in the acid component, .alpha.,.beta.-monoolefines with 2-4 C
atoms or conjugated diolefines with 4-6 C atoms.

3. Polymers according to claim 2, characterized in that 0.1-12% by weight of the copolymerized units of the monomers (B) consist of copolymer-ized units of at least one of the monomers divinylbenzene, diallyl phthalate, divinyl adipate, acrylic acid allyl ester or methacrylic acid allyl ester, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallyl (iso) cyanurate, and bis-acrylates or bis-methacrylates of glycols or polyglycols with 2-20 C atoms.

4. A process for complexing metal ions of the transition metals of the periodic system of the elements and of the metals magnesium, calcium, aluminium, lead, tin and bismuth which comprises reacting said metals or metal ions with a polymer of formula I as defined in claim 1.