Note: Descriptions are shown in the official language in which they were submitted.
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 -
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. , . ; ; . ~ ~ . .
~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
R R2
C = C
R1 C = O
~ I
H3C - C - CH3
~ '.
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 -
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~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 _
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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 -
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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 -
.
