Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
0050/51369 CA 02406651 2002-10-24
Polyelectrolyte complexes and their preparation
The invention relates to polyelectrolyte complexes of cationic
and anionic polymers, and to a process for their preparation.
It has been known for some time that cationic and anionic
polymers aggregate due to charge neutralization, forming comple-
xes which exhibit new properties, for example a phase or solubi-
lity behavior which is characteristic neither of the basic or
cation component nor of the acidic or anionic component.
EP-A 0 492 188 discloses, for example, complexes which are prepa-
red by mixing an aqueous solution of, for example, sodium poly-
methacrylate with an aqueous solution of ammonium compounds, such
dodecyltrimethylammonium bromide. The complexes act as sorbents
and are used, for example, for removing organic compounds from
effluent. The stability and water absorption capacity of comple-
xes is described, for example, in WO-A-96/02276 with respect to
the liberation of active compounds and in JP/A-62/112654 with
respect to papermaking.
WO-A-98/17762 discloses the use of polycationic condensation
products obtainable, for example, by condensation of piperazine,
substituted piperazines, imidazole or alkyl-substituted imidazo-
les with crosslinking agents as color transfer inhibitors and
color removal reducing additive for detergents and laundry after-
treatment agents. The condensation products may, if desired, also
be in quaternized form.
It is an object of the present invention to provide novel
substances whose cationic component is affected significantly
less by anionic compounds, such as surfactants, on use compared
with use of the cationic component of the complex alone.
We have found that this object is achieved in accordance with the
invention by polyelectrolyte complexes of cationic and anionic
polymers if they consist of
(a) cationic condensates of (i) at least one amine selected from
the group consisting of linear alkylamines, branched alkyla-
mines, cycloalkylamines, alkoxyamines, amino alcohols, cyclic
amines containing at least one nitrogen atom in a ring struc-
ture, alkylenediamines, polyetherdiamines, polyalkylenepolya-
mines, mixtures of one of the said amines with at least one
amino acid or a salt thereof, reaction products of the said
amines with at least one anionic group containing alkylating
agent wherein per mole of NH group of the amines of from 0.04
to 0.6 moles of the anionic group containing alkylating agent
0050/51369 CA 02406651 2002-10-24
2
is reacted, and mixtures thereof, and (ii) a crosslinking
agent from the group consisting of epihalohydrins, bishalohy-
drins of diols, bishalohydrins of polyalkylene glycols, bis-
halohydrins of polytetrahydrofurans, alkylene dihalides,
alkylene trihalides, bisepoxides, trisepoxides, tetraepoxides
and/or mixtures of said compounds, and/or quaternized
cationic condensates of. (i) and (ii), and
(b) anionic compounds containing at least three anionic groups
and in which the charge ratio between anionic and cationic
polymers is from 0.01 to 20.
Specific examples of the said amines are methylamine, ethylamine,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, pen-
tylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine,
isooctylamine, nonylamine, isononylamine, decylamine, undecyla-
mine, dodecyclamine, tridecylamine, stearylamine, palmitylamine,
dimethylamine, diethylamine, dipropylamine, dibutylamine, dipen-
tylamine, dihexylamine, bis-(2-ethyl-hexyl)amine, ditridecyla-
mine, N-methylbutylamine, N-ethylbutylamine, piperidine,
morpholine, pyrrolidine,
2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine,
3-ethoxypropylamine, 3-[(2-ethylhexyl)oxy]-1-propaneamine,
3-[(2-methoxyethoxy]-1-propaneamione, 2-methoxy-N-(2-methoxy-
ethyl)ethanamine,
2-azninoethanol, 3-amino-l-propanol, 1-amino-2-propanol, 2-(2-ami-
noethoxy)ethanol, 2-[(2-aminoethyl)amino]ethanol, 2-(methyl-
amino)ethanol, 2-(ethylamino)ethanol, 2-(butylamino)ethanol,
diethanolamine, 3-[(2-hydroxyethyl)amino]1-propanol, diisopropa-
nolamine, bis-(2-hydroxyethyl)aminoethylamine, bis-(2-hydroxy-
propyl)aminoethylamine, bis-(2-hydroxyethyl)aminopropyl-amine,
bis-(2-hydroxypropyl)aminopropylamine,
cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine,
N-ethylcyclohexylamine, dicyclohexylamine, ethylenediamine,
propylenediamine, butylenediamine, neopentyldiamine, hexa-
methylenediamine, octamethylenediamine, isophoronediamine,
4,4'-methylenebiscyclohexylamine, 4,4'-methylenebis(2-methylcy-
clohexylamine), 4,7-dioxadecyl-1,10-diamine, 4,9-dioxadode-
cyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine, 2-(ethyl-
amino)ethylamine, 3-(methylamino)propylamine, 3-(cyclohexyl-
amino)propylamine, 3-aminopropylamine, 2-(diethylamino)ethyla-
mine, 3-(dimethylamino)propylamine, 3-(diethylamino)propylamine,
0050/51369 CA 02406651" 2002-10-24
3
dipropylenetriamine, tripropylenetetramine, N,N-bis-(amino-
propyl)methylamine, N,N-bis-(aminopropyl)ethylamine, N,N-
bis-(aminopropyl)hexylamine, N,N-bis-(aminopropyl)octylamine,
1,1-dimethyldipropylenetriamine, N,N-bis-(3-dimethylamino-
propyl)amine, N,N " -1,2-ethanediylbis-(1,3-propanediamine), die-
thylenetriamine, bis-(aminoethyl)ethylenediamine, bis-(amino-
propyl)ethylenediamine, bis-(hexamethylene)triamine, N-(amino-
ethyl)hexamethylenediamine, N-(aminopropyl)hexamethylenediamine,
N-(aminopropyl)ethylenediamine, N-(aminoethyl)butylenediamine,
N-(aminopropyl)butylenediamine, bis-(aminoethyl)hexamethylenedi-
amine, bis-(aminopropyl)hexamethylenediamine, bis-(aminoethyl)bu-
tylenediamine, bis-(aminopropyl)butylenediamine, 4-aminomethyloc-
tane-1,8-diamine, and N,N-diethyl-1,4-pentanediamine.
Cyclic amines containing at least one nitrogen atom in a ring
structure are for example monoaminoalkylpiperazines, bis(amino-
alkyl)piperazines, monoaminoalkylimidazoles, aminoalkylmorpholi-
nes, aminoalkylpiperidines and aminoalkylpyrrolidines. The mono-
aminoalkylpiperazines are for example 1-(2-aminoethyl)piperazine
and 1-(3-aminopropyl)piperazine. Preferred monoaminoalkylimidazo-
les have 2 to 8 carbons atoms in the alkyl group. Examples of
suitable compounds are 1-(2-aminoethyl)imidazole and 1-(3-amino-
propyl)imidazole that. Suitable bis(aminoalkyl)piperazines are
for example 1,4- bis(-2-aminoethyl)piperazine and
1,4-bis(3-aminopropyl)-piperazine. Preferred aminoalkylmorpholi-
nes are aminoethylmorpholine and 4-(3-aminopropyl)-morpholine.
Other preferred compounds of this group are aminoethylpiperidine,
aminopropylpiperidine and aminopropylpyrrolidine.
Cyclic amines with at least two reactive nitrogen atoms in the
ring are for example imidazole, C-alkyl substituted imidazoles
having 1 to 25 carbon atoms in the alkyl group such as 2-methyl-
imidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimida-
zole and 2-isobutylimidazole, imidazoline, C-alkyl substituted
imidazolines having 1 to 25 carbon atoms in the alkyl group and
arylimidazolines such as 2-phenylimidazoline and 2-tolylimidazo-
line, piperazine, N-alkylpiperazines having 1 to 25 carbon atoms
in the alkyl group such as 1-ethylpiperazine, 1-(2-hy-
droxy-l-ethyl)piperazine, 1-(2-hydroxy-l-propyl)piperazine,
1-(2-hydroxy-l-butyl)piperazine, 1-(2-hydroxy-l-pentyl)pipera-
zine, 1-(2,3-dihydroxy-l-propyl)piperazine, 1-(2-hydroxy-3-phen-
oxyethyl)piperazine, 1-(2-hydroxy-2-phenyl-l-ethyl)piperazine,
N,N'-dialkylpiperazines having 1 to 25 carbon atoms in the alkyl
group for example 1,4-dimethylpiperazine, 1,4-diethylpiperazine,
1,4-dipropylpiperazine, 1,4-dibenzylpiperazine,
1,4-bis(2-hydroxy-l-ethyl)piperazine, 1,4-bis(2-hydroxy-l-pro-
.
0050/51369 CA 02406651 2002-10-24
4
pyl)piperazine, 1,4-bis(2-hydroxy-l-butyl)piperazine,
1,4-bis(2-hydroxy-l-pentyl)piperazine, and 1,4-bis(2-hy-
droxy-2-phenyl-l-ethyl)piperazine. Other cyclic amines with at
least two reactive nitrogen atoms are melamine and benzimidazoles
such as 2-hydroxybenzimidazole and 2-aminobenzimidazole.
Preferred cyclic amines with at least two reactive nitrogen atoms
are imidazole, 2-methylimidazole, 4-methylimidazole and
piperazine.
In a preferred embodiment of the invention the amine is selected
from the group consisting of (i) at least one cyclic amine con-
taining at least two reactive nitrogen atoms and (ii) mixtures of
at least one cyclic amine containing containing at least two
reactive nitrogen atoms with at least one other amine containing
1 to 6 nitrogen atoms. Examples of other amines containig 1 to 6
nitrogen atoms of which at least one is not quaternary are linear
alkyl amines having 1 to 22 carbon atoms in the alkyl group,
branched alkylamines, cycloalkylamines, alkoxyamines, amino alco-
hols, cyclic amines containing one nitrogen atom in a ring struc-
ture, alkylenediamines, polyether diamines, and polyalkylenepo-
lyamines containing 3 to 6 nitrogen atoms.
Preferred amines that are used in mixture with at least one cy-
clic amine with at least two reactive nitrogen atoms are methyl-
amine, ethylamine, propylamine, ethylenediamine, 1,4-diamino-
butane, 1,2-diaminobutane, 1,3-diaminopropane, 1,2-diamino-
propane, hexamethylenediamine, bishexamethylenetriamine, diethy-
lenetriamine, dipropylenetriamine, triethylentetramine, tetrae-
thylenepentamine, dimethylaminopropylamine and N,N-bis(3-amino-
propyl)-N-methylamine.
Most preferred amines that are used in mixture with at least one
cyclic amine with at least two reactive nitrogen atoms are
ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, dime-
thylaminopropylamine and N,N-bis(3-aminopropyl)-N-methylamine.
The term "reactive nitrogen atom" means that this nitrogen atom
is capable of reacting with for example an alkylating agent, e.g.
benzyl chloride, or with a crosslinker, e.g. ethylene chloride or
epichlorohydrin and excludes quaternary nitrogen atoms which can-
not react further. In accordance with the said meaning primary,
secondary and tertiary amino groups contain one reactive nitrogen
atom, whereas imidazole contains two.
0050/51369 CA 02406651 2002-10-24
The amines specified above can be used in mixture with at least
one amino acid or a salt thereof. Examples of amino acids are
glycine, alanine, aspartic acid, glutamic acid, asparagine, glut-
amine, lysine, arginine, threonine, 2-phenylglycine, 3-aminopro-
5 pionic acid, 4-aminobutyric acid, 6-aminocaproic acid, 11-ami-
noundecanoic acid, iminodiacetic acid, sarcosine, 1-carboxyme-
thylpiperazine, 1,4-bis(carboxymethyl)piperazine, 1-carboxymethy-
limidazole, imidazole carboxylic acid, anthranilic acid, sulfani-
lic acid, amidosulfonic acid, aminomethylsulfonic acid, aminoe-
thylsulfonic acid, salts thereof, and mixtures thereof. Prefera-
bly per one mole of reactive nitrogen groups in the amines 0.1 to
2 moles of amino acids are used.
Reaction products of the said amines with at least one anionic
group containing alkylating agent may be used as component (a) in
the process of the invention and are contained in condensed form
in the amphoteric amine based polymers having a net cationic
charge. Examples of anionic group containing alkylating agents
are 2-chloroacetic acid, 3-chloropropionic acid, 2-chloroethane-
sulfonic acid, epoxysuccinic acid, propane sultone,
3-chloro-2-hydroxypropanesulfonic acid, and mixtures thereof.
Other suitable anionic group containing alkylating agents are
monoethylenically unsaturated acids such as acrylic acid, meth-
acrylic acid, maleic acid, itaconic acid, and vinylsulfonic acid.
This group of alkylating agents reacts with the NH-goups of the
amines via Michael addition reaction. Per mole of the NH goups of
the amines 0.04 to 0.6 moles of the anionic group containing al-
kylating agent is used in the production of the amphoteric amine
based polymers having a net cationic charge.
A preferred group of polycationic condensation products of the
polyelectrolyte complexes is obtainable by condensation of
(i) piperazine, 1-alkylpiperazines having 1 to 25 carbon atoms in
the alkyl group, 1,4-dialkylpiperazines having 1 to 25 carbon
atoms in the alkyl groups, 1,4-bis(3-aminopropyl)piperazine,
1-(2-aminoethyl)piperazine, 1-(2-hydroxyalkyl)piperazines ha-
ving 2 to 25 carbon atoms in the alkyl group, imidazole, C1-
to C25-C-alkylimidazoles, aminoalcohols, linear, branched or
cyclic alkylamines, other alkylenediamines, polyetherdiami-
nes, polyalkylenepolyamines, or mixtures of said compounds
with
(ii) epichlorohydrin, bishalohydrins of C2- to C8-diols, bisglyci-
dyl ethers of C2- to C18-diols, bisglycidyl ethers of poly-
alkylene glycols, bisepoxybutane and/or alkylene dihalides
0050/51369 CA 02406651'2002-10-24
6
in a molar ratio of from 2 : 1 to 1: 1.5, and, if desired, qua-
ternization of the condensation products. The cationic component
of these polyelectrolyte complexes is disclosed, for example, in
WO-A-98/17762.
The polyelectrolyte complexes preferably comprise, as cationic
component (a), polycationic condensation products obtainable by
condensation of
(i) piperazine, 1-(2-hydroxyethyl)piperazine, 1-(2-amino-
ethyl)piperazine, imidazole, C1- to C3-C-alkylimidazoles,
or mixtures of said compounds with
(ii) 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropro-
pane, 1,4-dichlorobutane, epichlorohydrin, bischlorohydrin
ethers of diols, bischlorohydrin ethers of polyalkylene
glycols, bischlorohydrin ethers of polytetrahydrofurans,
bisepoxybutane, or mixtures of said compounds, and
(iii) quaternization of the condensation products with alkyl ha-
lides, epoxides, chloroacetic acid, 2-chloroethanesulfonic
acid, chloropropionic acid, epoxysuccinic acid, propane
sulfone, 3-chloro-2-hydroxypropanesulfonic acid, dimethyl
sulfate and/or diethyl sulfate, or oxidation of the ter-
tiary nitrogen atoms of the condensation products to N-oxi-
des.
Particular preference is given to polyelectrolyte complexes which
comprise, as cationic component (a), polycationic condensation
products obtainable by condensation of
(i) piperazine, imidazole or mixtures thereof with (ii)
epichlorohydrin, where the condensation products have mole-
cular weights Mw of from 500 to 1 million and have a charge
density of from 0.8 to 8 mequiv/g, and polyelectrolyte com-
plexes in which at least 80% of the NH groups in the
cationic component (a) are in quaternized form or as N-oxi-
des.
If the quaternization is carried out using quaternizing agents
containing an anionic group, such as chloroacetic acid or 2-chlo-
roethanesulfonic acid, it is only continued to the extent that
the quaternized amphoteric condensation products formed still
carry a net cationic charge. The charge density of the cationic
component is, for example, from 0.1 to 8, preferably from 0.5 to
7, milliequivalents/g. The molecular weights of the condensation
products are in the range from 500 to 1,000,000, preferably from
Y
0050/51369
7
1000 to 100,000. The amine-epichlorohydrin condensates carry at
least 3 cationic or potentially cationic, basic points per poly-
mer molecule. The charges can also be achieved after the conden-
sation by polymer-analogous reaction or by co-condensation of
epichlorohydrin with suitable amines.
Amphoteric polymers carrying a net cationic charge which are sui-
table as component (a) are obtainable, for example, by
(i) reacting at least 1 amine from the group consisting of li-
near alkylamines, branched alkylamines, cycloalkylamines,
alkoxyamines, aminoalcohols, cyclic amines having at least
1 nitrogen atom in the ring, alkylenediamines, polyether-
diamines, polyalkylenepolyamines, or mixtures of said
amines with alkylating agents containing at least one
anionic group, such as chloroacetic acid, in such a way
that the reaction products are substituted by from 0.04 to
0.6 mol of alkylating agents containing anionic groups per
mol of NH groups in the amines, and the reaction products
are subsequently
(ii) allowed to react with at least one crosslinking agent in an
(a) :(b) molar ratio of from 2: 1 to 1: 1.5. Thus, for
example, imidazole can firstly be reacted with
3-chloro-2-hydroxypropanesulfonic acid or chloroacetic acid
in aqueous solution at temperatures of, for example, from
60 to 100 C, and the reaction product is then crosslinked
with epichlorohydrin.
The charge ratio between the anionic and the cationic polymers in
the polyelectrolyte complexes is from 0.01 to 20, preferably from
0.1 to 5.
Suitable anionic group containing compounds (b) contain at least
three anionic groups, for example, polyacids such as citric acid,
butane tetracarboxylic acid, cyclopentane tetracarboxylic acid,
sulfoisophthalic acid and iminodisuccinic acid and polymers of
acid group containing monomers such as homopolymers and
copolymers of monoethylenically unsaturated C3- to Clo-carboxylic
acids or their anhydrides, for example acrylic acid, methacrylic
acid, acrylic anhydride, methacrylic anhydride, maleic acid,
maleic anhydride, fumaric acid, crotonic acid, itaconic acid,
itaconic anhydride, citraconic acid, mesaconic acid, methylenema-
lonic acid, 1,2,3,6-tetrahydrophthalic anhydride, 2-acryl-
amido-2-methylpropanesulfonic acid, allylsulfonic acid, methal-
lylsulfonic acid, vinylsulfonic acid, styrenesulfonic acid and
salts of the above monomers. The anionic monomers are soluble in
CA 02406651 2002-10-24
0050/51369
8
water or dissolve in partially or fully base-neutralized form. In
the present connection, the term "water-soluble monomers" is
taken to mean all anionic monomers which have a water-solubility
at 20 C of greater than 20 g/1. In order to prepare the salts of
the hydrophilic monomers, use is made, for example, of alkali
metal bases, alkaline earth metal bases and ammonia or amines.
Preferred salts of the hydrophilic monomers are the sodium and
potassium salts and the ammonium salts, which are obtainable by
neutralization of the acid groups of the monomers using, for
example, sodium hydroxide solution, potassium hydroxide solution
or ammonia.
Further suitable anionic polymers are homopolymers and copolymers
of, for example, monoesters of maleic acid and alcohols having 1
to 25 carbon atoms or monoamides of maleic acid.
Other suitable anionic polymers are copolymers of maleic
anhydride with C4- to C12-olefins, particularly preferably C8-ole-
fins, such as 1-octene and diisobutene. Very particular prefe-
rence is given to diisobutene. The molar ratio between maleic
anhydride and olefin is, for example, in the range from 0.9 : 1
to 3 : 1, preferably from 0.95 : 1 to 1.5 : 1. These copolymers
are employed in hydrolyzed form as an aqueous solution or disper-
sion, where the anhydride group is in opened form and some or all
of the carboxyl groups have preferably been neutralized. The fol-
lowing bases, for example, are employed for the neutralization:
alkali metal bases, such as sodium hydroxide, potassium hydro-
xide, sodium carbonate, potassium carbonate, alkaline earth metal
salts, such as calcium hydroxide, calcium carbonate, magnesium
hydroxide, ammonia, primary, secondary or tertiary amines, such
as triethylamine, triethanolamine, diethanolamine etc. If desi-
red, the preferred copolymers of maleic anhydride with C4-C12-ole-
fins can also be partially reacted polymer-analogously at the
anhydride function. To this end, alcohols or amines having 1 to
25 carbon atoms, furthermore also alkoxylated alcohols, for
example, are suitable.
Preferred anionic polymers (b) are homopolymers and copolymers of
monoethylenically unsaturated C3- to C8-carboxylic acids, homo-
polymers and copolymers of monomers containing sulfonic acid
groups, homopolymers and copolymers of monomers containing
phosphonic acid groups, water-soluble salts of said polymers, and
mixtures of said polymers.
The copolymers are prepared by known methods of free-radical
polymerization, such as solution polymerization, emulsion
polymerization, dispersion polymerization, precipitation
CA 02406651 2002-10-24
0050/51369 =
9
polymerization and melt polymerization. Suitable solvents or di-
luents are the conventional compounds, for example water, alco-
hols, ketones, esters, aliphatic compounds, aromatic compounds or
mixtures, for example water/isopropanol mixtures. The solvents or
diluents employed can also be one or more of the monomers, or the
use of a solvent or diluent can be omitted entirely. The polyme-
rizations can be carried out either as a batch reaction or with
one or more feeds. In this case, the feed times and the amounts
of individual components per time unit can be varied. This ena-
bles the parameters, such as copolymer composition, mean molecu-
lar weight or molecular weight distribution, to be controlled
characteristically.
Water-soluble polyanions have, for example, molecular weights Mw
of from 1000 to 10,000,000, preferably from 2000 to 500,000. Com-
ponent (b) of the polyelectrolyte complexes according to the in-
vention is, in particular, a polycarboxylic acid having a molecu-
lar weight MW of from 1000 to 250,000 in the unneutralized form,
partially neutralized form or fully neutralized form. Individual
examples of water-soluble anionic polymers (b) are the following:
polyacrylic acid having molecular weights of from 1000 to
250,000,
polymethacrylic acid having molecular weights of from 1000 to
250,000,
polymaleic acid having molecular weights of from 200 to 5,000,
copolymers or terpolymers of acrylic acid, methacrylic acid or
maleic acid, for example acrylic acid-methacrylic acid copolymers
having molecular weights of from 1000 to 100,000
acrylic acid-maleic acid copolymers having molecular weights of
from 1000 to 100,000
methacrylic acid-maleic acid copolymers having molecular weights
of from 1000 to 100,000
Other suitable copolymers are, for example, acrylonitrile, metha-
crylonitrile, styrene, methyl acrylate, methyl methacrylate,
ethyl methacrylate, hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate, alkylpolyethylene glycol (meth)acrylate, allyl
alcohol, acrylamide, methacrylamide, N-dimethylacrylamide, vinyl
acetate, vinyl propionate, vinyl phosphonate, allyl phosphonate,
N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, vinyl-
CA 02406651 2002-10-24
0050/51369
phosphonic acid. It is furthermore also possible to copolymerize
cationic copolymers in a secondary amounts (< 10% by weight) so
long as the copolymers formed carry a net anionic charge.
Examples of polymers which contain at least 10% by weight of
5 copolymerized unsaturated carboxylic acids are the following:
styrene-acrylic acid copolymers having molecular weights of from
1000 to 100,000
10 styrene-maleic acid copolymers having molecular weights of from
1000 to 100,000
olefin-maleic acid copolymers with C2- to C1500-olefins, for
example
isobutene-maleic acid copolymers having molecular weights of from
1000 to 10,000
diisobutene-maleic acid copolymers having molecular weights of
from 1000 to 10,000
C12-olefin-maleic acid copolymers having molecular weights of from
1000 to 10,000
C20/24-olefin-maleic acid copolymers having molecular weights of
from 1000 to 10,000
vinyl acetate-acrylic acid copolymers having molecular weights of
from 1000 to 100,000
vinyl acetate-maleic acid copolymers having molecular weights of
from 1000 to 100,000
vinyl acetate-acrylic acid-maleic acid terpolymers having molecu-
lar weights of from 1000 to 100,000
acrylamide-acrylic acid copolymers having molecular weights of
from 1000 to 100,000
polystyrene sulfonate having molecular weights of from 1000 to
250,000
Further anionic polymers are homocondensates and co-condensates
of aspartic acid and lysine, for example polyaspartic acid having
molecular weights M, of from 1000 to 100,000.
CA 02406651 2002-10-24
0050/51369 CA 02406651 2002-10-24
11
The present invention also relates to a process for the prepara-
tion of polyelectrolyte complexes by mixing cationic polymers
with anionic polymers. In accordance with the invention,
(a) cationic condensates of
(i) at least one amine and
(ii)a crosslinking agent from the group consisting of
epihalohydrins, bishalohydrins of diols, bishalohydrins
of polyalkylene glycols, bishalohydrins of polytetra-
hydrofurans, alkylene dihalides, alkylene trihalides, bi-
sepoxides, trisepoxides, tetraepoxides and/or mixtures of
said compounds, and
(b) anionic compounds containing at least three anionic groups.
The polyelectrolyte complexes can either be in the form of a mi-
croscopic or macroscopic 2nd phase in aqueous systems and for-
mulations or homogeneously dissolved. The polyelectrolyte comple-
xes are preferably prepared by combining aqueous solutions of the
cationic and anionic polymers, by introducing an anionic polymer
into a solution of a cationic polymer or by introducing a
cationic polymer into a solution of anionic polymers. However, it
is also possible to prepare polyelectrolyte complexes by mixing
anionic and cationic polymers in suitable joint solvents or in
the absence of solvents. However, the pclyelectrolyte complexes
are preferably prepared in aqueous medium. For the preparation of
the polyelectrolyte complexes, an aqueous solution containing
from 1 to 60% by weight, preferably from 2 to 55% by weight, of a
cationic condensate (a) in dissolved form, for example, is mixed
with a 1 to 60% strength by weight aqueous solution of an anionic
polymer (b). The aqueous solution of the anionic polymer prefera-
bly contains from 2 to 55% by weight of anionic polymer in
dissolved form.
The polyelectrolyte complexes are preferably prepared by turbu-
lent mixing. A further preferred embodiment for the preparation
of the polyelectrolyte complexes is a joint spraying of the
solution of a cationic condensate and the solution of an anionic
polymer.
Either homogeneous solutions or dispersions of polyelectrolyte
complexes are obtained. The mixing of the two polymers of diffe-
rent charge can be carried out, for example, in a stirred tank
reactor or in turbulent flow, for example in a nozzle. If the po-
lyelectrolyte complexes are in the form of a solution or disper-
0050/51369 CA 02406651 2002-10-24
12
sion, the diluents can be removed by, for example, spraying the
solutions or dispersions with evaporation of the solvent. Pulve-
rulent polyelectrolyte complexes are then obtained.
In the polyelectrolyte complexes, the charge ratio between
anionic and cationic polymers is from 0.01 to 20, preferably in
the range from 0.1 to 5.
The cationic component of the polyelectrolyte complexes has been
used for some time as an auxiliary in textile finishing and in
the after-treatment of washed textile goods. However, a broad
application in complex formulations in which a wide variety of
interactions of the constituents with one another can change the
mode of action of the individual formulation constituents is not
possible owing to the strong interaction of the cationic polymers
with the usually anionic dispersants, detergents or emulsifiers.
By contrast, complex formation between cationic and anionic
polymers results in an aggregate which is very stable, even in
very dilute media. A strong interaction with low-molecular-weight
anionic formulation constituents is prevented owing to charge in-
teractions in the complexes. By contrast, the action of the
cationic condensates remains comparable in the polyelectrolyte
complexes according to the invention. This gives rise to the pos-
sibility of incorporating the action of polycations into complex
formulations with a large number of possible interactions. On use
of the polyelectrolyte complexes in detergents or additives for
textile washing, textile care is obtained through which the out-
ward appearance, such as color impression, mechanical and micro-
mechanical properties, such as hardness, flexibility and tear
strength of filaments, fibers and fabrics, is improved. For fa-
bric care, the textile materials can also be impregnated, sprayed
or coated with solutions or dispersions of the complexes accor-
ding to the invention.
Examples
The charge densities were determined with the aid of colloid ti-
tration, cf. D. Horn, Progr. Colloid & Polymer Sci., Volume 65,
251-264 (1978).
Example 1
ml of an aqueous solution (100 mg/1, pH 10) of an imidazole-
epichlorohydrin condensate in a weight ratio of 1 : 1.4 (M, 8 kDa,
charge density 5.6 meq/g) were mixed with 50 ml of an aqueous
45 solution (50 mg/1, pH 10) of a polyacrylic acid (M,,õ 8 kDa, charge
density 11 meq/g), and the mixture was diluted to 300 ml with
0050/51369 CA 02406651 2002-10-24
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fully demineralized water and stirred for 5 minutes. A cloudy
solution of the charge-neutralized complex was formed.
Example 2
10 ml of an aqueous solution (500 mg/1, pH 10) of an imidazole-
epichlorohydrin condensate in a weight ratio of 1 : 1.4 (M, 100
kDa, charge density 5.6 meq/g) were mixed with 10 ml of an
aqueous solution (500 mg/l, pH 10) of a polyacrylic acid (Mw 8
kDa, charge density 11 meq/g), and the mixture was made up to 300
ml with fully demineralized water (pH 10) and stirred for 5 minu-
tes. A clear solution of the complex was formed.
Example 3
100 ml of an aqueous solution (500 mg/l, pH 10) of the imidazole-
epichlorohydrin condensate described in Example 2(M, 100 kDa,
charge density 5.6 meq/g) were mixed with 100 ml of an aqueous
solution (500 mg/l, pH 10) of a polyacrylic acid (M, 8 kDa, charge
density 11 meq/g), and the mixture was made up to 300 ml with
fully demineralized water (pH 10) and stirred for 5 minutes. A
clear solution of an anionic complex was formed.
Example 4
100 ml of an aqueous solution (500 mg/l, pH 10) of the imidazole-
epichlorohydrin condensate described in Example 2(Mw 100 kDa,
charge density 5.6 meq/g) were mixed with 50 ml of an aqueous
solution (100 mg/1, pH 10) of a polyacrylic acid (M,õ 8 kDa, charge
density 11 meq/g), and the mixture was made up to 300 ml with
fully demineralized water (pH 10) and stirred for 5 minutes. A
clear solution of a cationic complex was formed.
Example 5
100 ml of an aqueous solution (50 g/l, pH 7) of the imidazole-
epichlorohydrin condensate described in Example 2(M, 100 kDa,
charge density 5.6 meq/g) were mixed with a 100 ml of an aqueous
solution (50 g/l, pH 7) of a polyacrylic acid (M,õ 8 kDa, charge
density about 8 meq/g). A clear solution of an anionic complex
was formed.
Example 6
100 ml of an aqueous solution (5 g/1, pH 7, 10 g/min) of the imi-
dazole-epichlorohydrin condensate described in Example 2
(M, 100 kDa, charge density 5.6 meq/g) were forced through a
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nozzle into 100 ml of an aqueous solution (50 g/l, pH 7) of a po-
lyacrylic acid (M,õ 8 kDa, charge density about 8 meq/g). A clear
solution of an anionic complex was formed.
Example 7
100 ml of an aqueous solution (50 mg/l, pH 10) of a piperazine-
epichlorohydrin condensate in a weight ratio of 1 : 1 which had
been quaternized to the extent of 70 mol% with benzyl chloride
(M,,,,100 kDa, charge density 3 meq/g) were mixed with 100 ml of an
aqueous solution (50 mg/l, pH 10) of an acrylic acid-maleic acid
copolymer (M,õ 70 kDa, charge density about 12 meq/g) with stir-
ring. A slightly cloudy solution of an anionic complex was for-
med.
20
30
40
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