Anionic associative rheology modifiers
Description
The present invention relates to new associative rheology modifiers, their manufacture
and application.
Specific requirements are often placed on cosmetic, pharmaceutical and technical
compositions with regard to their rheological properties. They can often only be converted
to the desired application form using additives, so-called thickeners. Examples
of customary low molecular weight thickeners are, for example, alkali metal and alumi
num salts of fatty acids, fatty alcohols or waxes. However, depending on the field of
use of the preparation to be thickened, the use of known thickeners is often associated
with disadvantages. For example, the thickening effect of such thickeners may not be
satisfactory or their incorporation into the preparation may be hindered or completely
impossible, for example due to incompatibility. The provision of products with a com
plex profile of properties using the lowest possible fraction or the fewest possible differ
ent active substances often presents difficulties. For example, there is a need for poly
mers for cosmetic compositions which have good conditioning or film-forming properties
and at the same time may serve as thickeners for such compositions. In addition,
esthetic requirements are increasingly being placed on cosmetic and pharmaceutical
products by consumers. For example, with such products, a preference for clear formu
lations in the form of gels is currently observed. There is therefore a need for cosmeti
cally and pharmaceutically compatible polymers which are suitable for providing a certain
property profile with regard to sensory, setting capabilities and rheology.
In general, polymeric thickeners allow the viscosity to be adjusted depending on the
polymers' molecular weight. One disadvantage which often arises when using
polymers as thickeners for preparing more highly viscous or gel-like preparations is that
as the molecular weight of the polymer increases, its incorporation into the cosmetic
composition generally becomes more difficult, and that ultimately often only swelling of
the polymer is observed instead of the desired solution.
Polymeric rheology modifiers may be classified as either naturally, or synthetically
derived products. Examples of the former include starch, cellulose, alginate, and
proteins. These naturally occurring polymers incorporate building blocks of
polysaccharide units, or amino acids, to provide efficient, water soluble rheology
modifiers. Grafting of selected moieties onto the backbone of the more widely utilized
natural products, such as starch and cellulose, provides for numerous modified
versions of the products, developed to address specific application requirements.
Three general classes of acrylic-based synthetic polymers comprise a group of prod
ucts that have been utilized as rheology modifiers in various applications for many
years. The first class is based on homopolymers of (meth)acrylic acid and copolymers
of (meth)acrylic acid, (meth)acrylate esters, and maleic acid, among many others. This
group is typically referred to as the alkali swellable (or soluble) emulsions (ASE).
Modification of the structure of ASE polymers by addition of hydrophobic moieties de
fines the second class of synthetic rheology modifiers known as the hydrophobically
modified, alkali swellable emulsions (HASE). This group of polymers, more commonly
referred to as associative thickeners, provides the potential for greater control of the
compound rheology, over a broader range of shear rates than the traditional ASE class
of synthetic polymers. The third class of synthetic rheology modifiers is the hydrophobi
cally modified, ethoxylated urethane resins (HEUR). This group of polymers typically
consists of polyethylene glycol units of varying length, connected by urethane linkages,
and terminated with hydrophobic end groups. Unlike the ASE and HASE classes,
HEUR rheology modifiers are nonionic substances, and are not dependent on pH for
activation of the thickening mechanism.
WO 93/22358 (BASF) describes copolymers obtainable by free-radical polymerization
of A) 50-99.99% by weight of an olefinically unsaturated C3-C5 monocarboxylic acid, of
an olefinically unsaturated C4-C8 dicarboxylic acid or the anhydride thereof or a mixture
of such carboxylic acids or anhydrides with B) 0.1-29.95% by weight of an olefinically
unsaturated quaternary ammonium compound of the formula I or I I
where R is C 6-C20 -alkyl, C 6-C20 -alkenyl, C 5 -Cs-cycloalkyl, phenyl, phenyl(Ci-Ci2-
alkyl) or (Ci-Ci2-alkyl)phenyl, R2 is hydrogen, methyl or phenyl, R3 and R4 are each H
or C1-C4 -alkyl, X is halogen, Ci -C4 -alkoxysulfonyloxy or Ci -C4 -alkanesulfonate, it also
being possible for the latter to occur as R3 or R4 with the formation of a betaine struc
ture, Y is O or NH, and A is C1-C6 -alkylene, or a mixture of such ammonium compounds,
C) 0 to 49.99% by weight of an acrylate or methacrylate of the formula III
H2 = C CH2 o ~
where R , R2 and Y have the aforementioned meanings, R5 is hydrogen, methyl or
ethyl, and n is a number from 0 to 25, D) 0-29.85% by weight of other copolymerizable
monomers and E) 0.5-2% by weight of one or more compounds with at least two olefinically
unsaturated groups in the molecule as crosslinker.
WO 00/39176 (BF Goodrich) describes a hydrophilic ampholytic polymer formed by
copolymerization of 0.05 to 20 mole percent of an anionic monomer having at least one
carboxyfunctional group, 10 to 45 mole percent of a cationic monomer having at least
one aminofunctional group, 35 to 95 mole percent of a nonionic hydrophilic monomer, 0
to 10 mole percent of a hydrophobic monomer and 0 to 1.5 mole percent of a crosslinking
monomer, and wherein the monomers are selected so as to provide the copolymer
with a glass transition temperature of above about 50°C and the cationic monomer and
the anionic monomer are present in a ratio of from about 2 to about 16.
WO 01/62809 (BASF) describes cosmetic compositions comprising at least one watersoluble
or water-dispersible polymer which comprises, in incorporated form, a) 5 to
50% by weight of at least one ,-ethylenically unsaturated monomer of the formula I
in which R is hydrogen or Ci- to Cs-alkyl, and X1 is O or NR2, where R2 is hydrogen,
Ci- to Cs-alkyl or Cs-to Cs-cycloalkyl, b) 25 to 90% by weight of at least one Nvinylamide
and/or N-vinyllactam, c) 0.5 to 30% by weight of at least one compound
having a free-radically polymerizable, ,-ethylenically unsaturated double bond and at
least one cationogenic and/or cationic group per molecule, d) 0 to 30% by weight of at
least one ,-ethylenically unsaturated monomer of the formula I I
R
C 2 — C — — }
t i
0
in which R3 is hydrogen or Ci- to Cs-alkyl, X2 is O or NR5, where R5 is hydrogen Ci- to
Cs-alkyl or Cs-to Cs-cycloalkyl, and R4 is hydrogen or a linear Ci- to C22 -alkyl radical
and the salts thereof.
WO 03/053381 (BASF) describes cosmetic compositions which comprise at least one
water-soluble or water-dispersible copolymer which is obtainable by free-radical copolymerization
of at least one N-vinyllactam, at least one anionogenic monomer and
optionally further a,-ethylenically unsaturated compounds copolymerizable therewith,
in the presence of a polymer component with repeat units which have ether groups or
which are derived from vinyl alcohol.
WO 2004/058837 (BASF) describes cosmetic or pharmaceutical compositions compris
ing A) at least one ampholytic copolymer obtainable by free-radical copolymerization of
a) at least one compound with a free-radically polymerizable, ,-ethylenically unsatu
rated double bond and at least one anionogenic and/or anionic group per molecule, b)
at least one compound with a free-radically polymerizable, ,-ethylenically unsatu
rated double bond and at least one cationogenic and/or cationic group per molecule, c)
at least one ,-ethylenically unsaturated amide-group-containing compound of the
formula R -CO-NR 2R3 in which one of the radicals R to R3 is a group of the formula
CH2=CR 4, where R4= H or Ci-C4-alkyl, and the other radicals R to R3, independently
of one another, are H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, where R and
R2 together with the amide group to which they are bonded may also be a lactam with
5 to 8 ring atoms, where R2 and R3 together with the nitrogen atom to which they are
bonded may also be a five-to seven-membered heterocycle, with the proviso that the
sum of the carbon atoms of the radicals R , R2 and R3 is at most 8, or a polyelectrolyte
complex comprising at least one of said ampholytic copolymers and at least one further
polyelectrolyte different therefrom, and B) at least one cosmetically acceptable carrier.
WO 2006/0441 93 (ISP) and US 2007/0231 286 A 1 (ISP) describe a rheology modi
fier/hair styling resin which is a crosslinked, linear polyvinyl amide/polymerizable car
boxylic acid) copolymer and its use in color cosmetic compositions.
WO 2007/01 0035 A 1 (BASF) describes the use of an anionic or cationic ampholytic
copolymer which is obtainable by free-radical copolymerization of a 1) at least one
compound having a free-radically polymerizable, ,-ethylenically unsaturated double
bond and at least one anionogenic and/or anionic group per molecule, a2) at least one
compound having a free-radically polymerizable, ,-ethylenically unsaturated double
bond and at least one cationogenic and/or cationic group per molecule, b) at least one
free-radically polymerizable crosslinking compound which contains at least two ,-
ethylenically unsaturated double bonds per molecule, c) if desired in the presence of at
least one silicone compound containing a polyether group and/or a free-radically poly
merizable olefinically unsaturated double bond, as rheology modifiers for compositions
in hair cosmetics.
US 4,230,844 (DuPont) describes thickener polymers comprising (i) about 1-99% by
weight of at least one unsaturated carboxylic acid of 3 to 6 carbon atoms, and (ii) about
1-99% by weight of at least one ester of the formula
wherein R and R2 are each hydrogen or methyl, x is a positive integer of 5 to 80, y is an
integer of 0 to 20, and Ri is alkyl of 1 to 20 carbon atoms or alkyl phenyl where the
alkyl group is from 1 to 20 carbon atoms or alkyl phenyl where the alkyl group is from 1
to 20 carbon atoms.
US 4,138,381 (Du Pont) describes thickeners comprising a polymer dissolved in a solvent
at a concentration up to 50% by weight of the composition, the solvent being at
least one glycol and containing during manufacture up to 50% by weight, based on the
weight of glycol, of water and the polymer consists essentially of (a) about 10 to 98%
by weight of at least one unsaturated carboxylic acid of 3 to 6 carbon atoms, (b) about
1 to 50% by weight of at least one alkyl acrylate or alkyl methacrylate wherein the alkyl
group is from 1 to 30 carbon atoms, and (c) about 1 to 85% by weight of at least one
ester of the formula
wherein R and R2 are each hydrogen or methyl, x is a positive integer of 5 to 80, y is an
integer of 0 to 20, and Ri is alkyl of 1 to 20 carbon atoms or alkyl phenyl where the
alkyl group is from 1 to 20 carbon atoms, the total adding up to 100%.
US 5,015,708 describes non-crosslinked precipitation terpolymer products produced by
polymerizing a reaction mixture of a vinyl lactam, e.g. vinyl pyrrolidone or vinyl
caprolactam, a polymerizable carboxylic acid, e.g. acrylic acid or methacrylic acid, and
a hydrophobic monomer, e.g. lauryl methacrylate, in a predetermined compositional
range, in the presence of a polymerization initiator, and in an aliphatic hydrocarbon
solvent, particularly a C 3 -C10 saturated hydrocarbon, which is branched or unbranched,
cyclic or acylic, and, preferably, is heptane or cyclohexane. The terpolymers are ob
tained in high yield, as a white powder, which can be filtered and dried easily.
US 6,025,431 describes a polymeric rheology modifier (PRM) which has been prepared
by polymerizing from about 5 to about 80 weight percent of an acrylate monomer
(a) selected from the group consisting of a C1-C6 alkyl ester of acrylic acid and a C1-C6
alkyl ester of methacrylic acid, from about 5 to about 80 weight percent of a monomer
(b) selected from the group consisting of a vinyl-substituted heterocyclic compound
containing at least one of a nitrogen or a sulfur atom, (meth)acrylamide, a mono- or di-
(Ci-C4)alkylamino (Ci-C4)alkyl (meth)acrylate and a mono or di-(Ci-C 4) alkylamino (CiC
4)alkyl (meth)acrylamide, and 0 to about 30 weight percent of an associative mono
mer (c), all percentages based on the total weight of monomer used to prepare the
PRM, and a cosmetically-active agent (CAA).
EP 3235 A 1 (BASF) describes a water-soluble copolymer which comprises (a) from 80
to 2% by weight of an ethylenically unsaturated C3- to C5-carboxylic acid, acrylamidodimethylpropanesulfonicacid,
vinylsulfonic acid or vinylphosphoric acid, or of an es
ter of the formula
where R is H or-CH3, n is from 1 to 4 and R and R2 are alkyls of 1 to 4 carbon atoms,
or of mixtures of the said monomers, and (b) from 20 to 98% by weight of a polymerizable
ethylenically unsaturated compound of the formula
H,
3_ CH -CH -0i -iCH -CH-0) m- C C CH
where R3 is alkyl of 1 to 20 carbon atoms, R4 is H or -CH3, R5 is H, n is from 2 to 100
and m is from 0 to 50.
EP 11806 A 1 (Dow Chemical) describes aqueous liquid emulsion polymers prepared
by the copolymerization of (A) 15-60 weight percent of a C3-C8 ,-ethylenically un
saturated carboxylic acid monomer, preferably acrylic or methacrylic acid or a mixture
thereof with itaconic or fumaric acid, (B) 15-80 weight percent of a nonionic copolymerizable
C2-C12 ,-ethylenically unsaturated monomer, preferably a monovinyl ester
such as ethyl acrylate or a mixture thereof with styrene, acrylonitrile, vinyl chloride or
vinyl acetate, and (C) 1-30 weight percent of certain nonionic vinyl surfactant esters,
such as nonylphenoxypoly(ethyleneoxy)g ethyl acrylate, to give an emulsion copolymer
stable as an aqueous colloidal dispersion at an acid pH lower than about 5.0 but responsive
to pH adjustment with base. These emulsion polymers adjusted to a pH of
5.5-10.5 or higher serve as thickeners for aqueous systems including cosmetic prod
ucts, drilling muds, and particularly aqueous coating compositions such as latex paint.
EP 13836 (Rohm & Haas) describes copolymers containing (1) 20-69.5% by weight of
acrylic and/or methacrylic acid; (2) 0.5-25% by weight of monomer of the formula
CH2=C(R)-C(0)-0 -(CH2CH 20)n-R0 wherein R is H or CH3, n is at least 2 and R° is C8-
C30 alkyl, alkylaryl or polycyclic alkyl; (3) at least 30% by weight of at least one Ci-C 4
alkyl acrylate and/or methacrylate and (4) 0-0.1 % by weight of polyethylenically unsatu
rated monomer, the total of (1), (2), (3) and (4) being 100%.
EP 1690878 A 1 (Rohm & Haas) describes a polymer comprising (a) from 25% to 45%
carboxylic acid monomer residues, (b) from 50% to 65% C 2 -C4 alkyl (meth)acrylate
residues, (c) from 2% to 20% of residues of at least one of: (i) an alkyl (meth)acrylate,
(ii) a vinyl alkanoate, (iii) an N-vinyl alkylamide, and (iv) an N-alkyl (meth)acrylamide,
wherein an alkyl group having from 6-18 carbon atoms is present; and (d) from 0.01 %
to 2% of residues of at least one crosslinker.
Anionic associative rheologiy modifying polymers are commercially available as e.g.
Aculyn ®22 (INCI: Acrylates/Steareth-20 Methacrylate Copolymer; a copolymer of the
ester of methacrylic acid and Steareth-20 and one or more monomers of acrylic acid,
methacrylic acid or one of their simple esters), Aculyn ®28 (INCI: Acrylates/Beheneth-25
Methacrylate Copolymer; a copolymer of the ester of methacrylic acid and Beheneth-25
and one or more monomers of acrylic acid, methacrylic acid, or one of their simple esters)
, Aculyn ®88 (INCI: Acrylates/Steareth-20 Methacrylate Crosspolymer; a copolymer
of steareth-20 methacrylate and one or more monomers consisting of acrylic acid,
methacrylic acid or one of their simple esters, crosslinked with an allyl ether of pentaerythritol
or an allyl ether of trimethylolpropane), and Tinovis ®GTC (INCI: Acry
lates/Beheneth-25 Methacrylate Copolymer).
Although there are plenty of polymeric thickeners for cosmetic use already known and
commercially available, there is still a need for thickeners that at the same time can
easily be incorporated into cosmetic compositions, enable fast thickening, particularly
at pH values in the ranges from 5 to 9, preferrably from 6 to 8, and have good film
forming and hair-setting properties. Furthermore, long-term stability of such cosmetic
compositions combined with tolerance of comparably high salt contents are desired
properties of up-to-date polymeric thickeners. Other desired properties are the ability to
form clear gels, stabilizing properties for particles, emulsions, and foams, broad pH
range stability, peroxide compatibility, shear tolerance, cold-processable, and broad
compatibility with other ingredients.
Surprisingly, it has now been found that these objects are achieved by a polymer com
prising as polymerized units
a) 25 to 85 % by weight of acrylic acid,
b) 10 to 60 % by weight of N-vinyl pyrrolidone,
c) 0.5 to 10 % by weight of at least one cationic monomer,
d) 0.5 to 20 % by weight of at least one of compounds d 1) or d2)
H 2 C = C C (CH 2 C H 2 O ) k (CH 2 CH(CH 3 )O), R
(d1 )
H 2 C=CH C H 2 O (CH 2 C H 2 O ) k (CH 2 C H (CH3)O), R
(d2)
wherein
the order of the alkylene oxide units is arbitrary,
k and I, independently of one another, are an integer of from 0 to 1000, where the
sum of k and I is at least 5,
R8 is hydrogen or Ci-C4 -alkyl, preferably methyl,
R9 is Cs-Cso -alkyl, Cs-Cso -alkenyl or C8-C30 alkylaryl, and
X is O or a group of the formula NR 0 , in which R 0 is H, alkyl, alkenyl,
cycloalkyl, heterocycloalkyl, aryl or hetaryl,
e) 0.01 to 2 % by weight of at least one crosslinking agent,
f) 0 to 30 % by weight of further monomers different from a) to e),
the total of a) to f) adding up to 100 % by weight.
For the purposes of this invention, the term "alkyl" comprises straight-chain and
branched alkyl groups. Suitable short-chain alkyl groups are, for example, straightchain
or branched CrC 7-alkyl groups, preferably CrC 6-alkyl groups and particularly
preferably CrC 4-alkyl groups. These include, in particular, methyl, ethyl, propyl, isopropyl,
n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-
methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl,
n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl,
1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,
3,3-dimethylbutyl, 1, 1 ,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl,
1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl.
Suitable longer-chain C 8- C 3o-alkyl groups and C 8- C 3o-alkenyl groups are straight-chain
and branched alkyl groups and alkenyl groups. Preference is given here to predomi
nantly linear alkyl radicals as also occur in natural or synthetic fatty acids and fatty a l
cohols and in oxo alcohols, which may, if appropriate, additionally be mono-, di- or
polyunsaturated. These include, for example, n-hexyl(ene), n-heptyl(ene), n-octyl(ene),
n-nonyl(ene), n-decyl(ene), n-undecyl(ene), n-dodecyl(ene), n-tridecyl(ene), ntetradecyl(
ene), n-pentadecyl(ene), n-hexadecyl(ene), n-heptadecyl(ene), noctadecyl(
ene), n-nonadecyl(ene), arachinyl(ene), behenyl(ene), lignocerinyl(ene),
melissinyl(ene).
Cycloalkyl is preferably C5-C8-cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl
or cyclooctyl.
Aryl comprises unsubstituted and substituted aryl groups and is preferably phenyl, tolyl,
xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in pa r
ticular phenyl, tolyl, xylyl or mesityl.
In the text below, compounds which are derived from acrylic acid and methacrylic acid
may sometimes be referred to in short by adding the syllable "(meth)" to the compound
derived from acrylic acid.
Monomer a)
In one embodiment of the invention the polymer comprises as polymerized units of
from 25 to 80 % by weight of acrylic acid.
In another embodiment of the invention the polymer comprises as polymerized units of
from 40 to 70 % by weight of acrylic acid.
In another embodiment of the invention the polymer comprises as polymerized units of
from 40 to 60 % by weight of acrylic acid.
Monomer b)
In one embodiment of the invention the polymer comprises as polymerized units of
from 10 to 60 % by weight of N-vinyl pyrrolidone.
In another embodiment of the invention the polymer comprises as polymerized units of
from 20 to 50 % by weight of N-vinyl pyrrolidone.
In another embodiment of the invention the polymer comprises as polymerized units of
from 30 to 50 % by weight of N-vinyl pyrrolidone.
Monomer c)
In one embodiment of the invention the polymer comprises as polymerized units of
from 1 to 10 % by weight of at least one cationic monomer.
According to this invention the term "cationic monomer" means monomers carrying a
cationic charge or monomers carrying groups, prefarably amine groups, that can be
cationically charged either by protonation or by quaternization with acids or alkylating
agents, respectively. In other words, the term "cationic monomer" refers to both cationi
cally charged monomers and monomers that can be cationically charged.
In one embodiment of the invention monomer c) comprises at least one compound
which is chosen from esters of ,-ethylenically unsaturated mono- and dicarboxylic
acids with amino alcohols which may be mono- or dialkylated on the amine nitrogen,
amides of ,-ethylenically unsaturated mono- and dicarboxylic acids with diamines
which have at least one primary or secondary amino group, N,N-diallylamine,
N,N-diallyl-N-alkylamines and derivatives thereof, vinyl- and allyl-substituted nitrogen
heterocycles, vinyl- and allyl-substituted heteroaromatic compounds and mixtures
thereof.
Preferred monomers c) are N-tert-butylaminoethyl (meth)acrylate,
,-dimethylaminomethyl (meth)acrylate, ,-dimethylaminoethyl (meth)acrylate,
,-diethylaminoethyl (meth)acrylate, ,-dimethylaminopropyl (meth)acrylate,
,-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl
(meth)acrylate. Particular preference is given to N-tert-butylaminoethyl (meth)acrylate
and ,-dimethylaminoethyl (meth)acrylate.
Other preferred monomers c) are, for example, N-[tertbutylaminoethyl(
meth)acrylamide, N-[2-dimethylamino)ethyl]acrylamide, N-[2-
(dimethylamino)ethyl]methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-
(dimethylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N-[4-
(dimethylamino)butyl]methacrylamide, N-[2-(diethylamino)ethyl]acrylamide, N-[4-
(dimethylamino)cyclohexyl]acrylamide and N-[4-
(dimethylamino)cyclohexyl]methacrylamide. Particular preference is given to
N-[3-(dimethylamino)propyl]acrylamide and N-[3-(dimethylamino)propyl]methacrylamide
(DMAPMAM).
A specific embodiment relates to polymers which comprise as monomer c) N-[3-
dimethylamino)propyl](meth)acrylamide. In another embodiment, monomer c) consists
of N-[3-(dimethylamino)propyl](meth)acrylamide.
Other preferred monomers c) are ,-diallylamines and N,N-diallyl-N-alkylamines and
acid addition salts thereof and quaternization products. Alkyl here is preferably
CrC 24-alkyl. Preference is given to N,N-diallyl-N-methylamine and N,N-diallyl-
,-dimethylammonium compounds, such as, for example, the chlorides and bro
mides. Particular preference is given to N,N-diallyl-N-methylamine.
Other preferred monomers c) are vinyl- and allyl-substituted nitrogen heterocycles d if
ferent from vinylimidazoles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and
the salts thereof.
In a preferred embodiment of the invention monomer c) comprises as vinyl-substituted
heteroaromatic compound c) at least one N-vinylimidazole compound.
In a specific embodiment of the invention monomer c) is chosen from N-vinylimidazole
compounds and mixtures which comprise at least one N-vinylimidazole compound.
In one embodiment of the invention at least one cationic monomer c) is chosen from
vinylimidazole compounds of the general formula (II)
(II)
wherein R5 to R7, independently of one another, are hydrogen, CrC 4-alkyl or phenyl.
Examples of compounds c) of the general formula (II) are given in Table 1 below:
Table 1
Ph = phenyl
In a preferred embodiment of the invention, monomer c) is selected from 1-
vinylimidazole (N-vinylimidazole) and mixtures comprising N-vinylimidazole.
A particularly preferred embodiment of the invention relates to polymers in which
monomer c) consists of N-vinylimidazole.
In one embodiment of the invention the polymer comprises as polymerized units of
from 0.5 to 10 % by weight of at least one cationic monomer c).
In another embodiment of the invention the polymer comprises as polymerized units of
from 1 to 4 % by weight of at least one cationic monomer c).
In another embodiment of the invention the polymer comprises as polymerized units of
from 2 to 6 % by weight of at least one cationic monomer c).
In one embodiment of the invention the molar ratio between monomer a) and monomer
c) is at least 4:1 . In another embodiment of the invention the molar ratio between
monomer a) and monomer c) is at least 10:1 . In still another embodiment of the inven
tion the molar ratio between monomer a) and monomer c) is at least 14:1 . In still another
embodiment of the invention the molar ratio between monomer a) and monomer
c) is at least 22:1 .
In one embodiment of the invention the molar ratio between monomer a) and monomer
c) is at most 110:1 . In another embodiment of the invention the molar ratio between
monomer a) and monomer c) is at most 80:1 . In another embodiment of the invention
the molar ratio between monomer a) and monomer c) is at most 50:1 .
In a preferred embodiment of the invention the molar ratio between monomer a) and
monomer c) is in the range of from 4:1 to 110:1 , more preferred in the range of from
10:1 to 80:1 , still more preferred in the range of from 14:1 to 50:1 .
Preferably, the cationogenic and/or cationic groups of the monomer c) are nitrogencontaining
groups, such as primary, secondary and tertiary amino groups, and quater
nary ammonium groups. The nitrogen-containing groups are preferably tertiary amino
groups or quaternary ammonium groups. Charged cationic groups can be produced
from the amine nitrogens either by protonation with acids or by quaternization with alky
lating agents. The acids include, for example, carboxylic acids, such as lactic acid, or
mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid. Alkylating
agents are e.g. CrC 4-alkyl halides or sulfates, such as ethyl chloride, ethyl bromide,
methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. A protonation or
quaternization can generally take place either before or preferably after the polymeriza
tion.
In one embodiment of this invention, monomers c) are co-polymerized in their nonquaternized
form and remain non-quaternized after the polymerization.
In another embodiment of this invention, monomers c) are co-polymerized in their nonquaternized
form and at partly quaternized after the polymerization.
In still another embodiment of this invention, monomers c) are co-polymerized in their
non-quaternized form and completely quaternized after the polymerization.
However, due to various experimental reasons, there can always be minor portions of
monomers c) that are already cationic (i.e. protonated or quaternized) before or during
the polymerization although no purposeful protonation/quaternization has been per
formed.
For reasons of simplicity, throughout this invention the names of the non-ionic, i.e. un
charged monomers c) like e.g. "N-vinylimidazole", "N-[3-
(dimethylamino)propyl](meth)acrylamide" or "N,N-diallylamine" stand for both the un
charged and the cationically charged monomers c).
Monomer d)
The polymers according to this invention comprise as polymerized units of from 0.5 to
10 % by weight of at least one of compounds d1) or d2). In one preferred embodiment
of this invention the polymers comprise as polymerized units of from 1 to 6 % by weight
of at least one of compounds d1) or d2). In still another preferred embodiment of this
invention the polymers comprise as polymerized units of from 2 to 4 % by weight of at
least one of compounds d1) or d2).
O
H 2 C : (CH 2 C H 2 O ) k (CH 2 CH(CH 3 )O),
(d1 )
H C=CH C H 2 O (CH 2 C H 2 O ) k (CH 2 C H (CH3)O), R
(d2)
wherein
the order of the alkylene oxide units is arbitrary,
k and I, independently of one another, are an integer from 0 to 1000, where the sum of
k and I is at least 5,
R8 is hydrogen or Ci-C4 -alkyl, preferably methyl,
R9 is Cs-Cso -alkyl, Cs-Cso -alkenyl or C8-C30 alkylaryl, and
X is O or a group of the formula NR 0 , in which R 0 is H, alkyl, alkenyl, cycloalkyl,
heterocycloalkyl, aryl or hetaryl.
In one preferred embodiment of the invention, R8 is hydrogen, methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, particularly preferred hydro
gen, methyl or ethyl. Most preferably R is methyl.
In one preferred embodiment of the invention, k is an integer in the range of from 1 to
500, in particular of from 3 to 250 and I is an integer in the range of from 0 to 100.
In one preferred embodiment of the invention, R of monomers d 1) and d2) is selected
from n-octyl, 1, 1 ,3,3-tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, tridecyl,
myristyl, pentadecyl, palmityl, heptadecyl, octadecyl, nonadecyl, arrachinyl, behenyl,
lignocerenyl, cerotinyl, melissinyl, palmitoleinyl, oleyl, linolyl, linolenyl, stearyl, lauryl.
In particularly preferred embodiments of this invention R of monomers d 1) and d2) is
selected from palmityl, heptadecyl, octadecyl, nonadecyl, arrachinyl, behenyl and their
binary or tertiary mixtures. In another preferred embodiment of this invention R of
monomers d 1) and d2) is selected from the binary and tertiary mixtures of the evennumbered
alkyl residues like e.g. C 6, C 8, C2o, and C22-
Preferably, X in formula d 1) is O or NH.
Suitable polyether (meth)acrylates d1) are, for example, the condensation products of
(meth)acrylic acid with polyetherols. Suitable polyetherols can be prepared easily by
reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrin with a starter alco
hol R9-OH. The alkylene oxides can be used individually, alternately one after the other
or as a mixture. The polyether (meth)acrylates d1) can be used on their own or in mix
tures for the preparation of the polymers according to the invention.
In one embodiment of this invention the polymers according to this invention comprise
as polymerized units at least one compound d1) chosen from polyether (meth)acrylates
terminated with Cs-C22-alkyl groups.
Preferred monomers d1) according to this invention are esters of methacrylic acid with
ethoxylated C16-C18 alkyl alcohols, wherein the degree of ethoxylation (k in formula d1))
is 10 to 40, preferably 20 to 30.
In one particularly preferred embodiment of the invention, the commercially available
C18 -PEG 1100 MA (Plex ®6877-0, CAS number 70879-51-5 (APG 1100 MA), manufac
turer: Degussa) is selected as at least one monomer d1).
In another embodiment of the invention, monomer d1) can be prepared as described in
U.S. Pat. No. 3,708,445 using alcohols and acids described in column 3, lines 36-75.
This particular monomer d1) is of the formula:
wherein R8 is hydrogen or methyl,
k is a positive integer of 5 to 80, preferably 10 to 50, and
R9 is alkyl of 8 to 15 carbon atoms or alkyl phenyl wherein the alkyl group is from 8 to
20 carbon atoms, preferably
wherein R 0 is alkyl of 8 to 20 carbon atoms.
Suitable allyl alcohol alkoxylates d2) are, for example, the etherification products of allyl
chloride with corresponding polyetherols. Suitable polyetherols can be prepared easily
by reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrin with water or a
starter alcohol R -OH. The alkylene oxides can be used individually, alternately one
after the other or as a mixture. The allyl alcohol alkoxylates d2) can be used on their
own or in mixtures for the preparation of the polymers according to this invention.
Monomer e)
The polymers according to this invention comprise in copolymerized form of from 0.01
to 2 % by weight of at least one crosslinking agent (crosslinker) e), i.e. a compound
with two or more ethylenically unsaturated, nonconjugated double bonds.
Suitable crosslinkers e) are e.g. (meth)acrylic esters, allyl ethers or vinyl ethers of at
least dihydric alcohols. The OH groups of the parent alcohols here may be completely
or partially etherified or esterified; however, the crosslinkers comprise at least two
ethylenically unsaturated groups.
Examples of the parent alcohols are dihydric alcohols, such as 1,2-ethanediol,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,
1,4-butanediol, but-2-ene-1 ,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol,
1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol,
3-methylpentane-1 ,5-diol, 2,5-dimethyl-1 ,3-hexanediol,
2,2,4-trimethyl-1 ,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,
1,4-bis(hydroxymethyl)cyclohexane, hydroxypivalic neopentyl glycol monoester,
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene
glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol,
tetrapropylene glycol, 3-thiopentane-1 ,5-diol, and polyethylene glycols, polypropyl
ene glycols and polytetrahydrofurans with molecular weights of in each case 200 to
10000. Apart from the homopolymers of ethylene oxide and propylene oxide also block
copolymers of ethylene oxide or propylene oxide or copolymers which comprise incor
porated ethylene oxide and propylene oxide groups can be used. Examples of parent
alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol,
1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars, such
as sucrose, glucose, mannose. The polyhydric alcohols can also be used following
reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or
propoxylates. The polyhydric alcohols can also firstly be converted into the corresponding
glycidyl ethers by reaction with epichlorohydrin. Preference is given to ethylene
glycol di(meth)acrylate and polyethylene glycol di(meth)acrylates.
Further suitable crosslinkers e) are the vinyl esters or the esters of monohydric, unsatu
rated alcohols with ethylenically unsaturated C3-C6-carboxylic acids, for example acrylic
acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such
alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl
alcohol, 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-
9-octadecen-1-ol. However, it is also possible to esterify the mono-hydric, unsaturated
alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic
acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
Further suitable crosslinkers e) are esters of unsaturated carboxylic acids with the
above-described polyhydric alcohols, for example of oleic acid, crotonic acid, cinnamic
acid or 10-undecenoic acid.
Suitable crosslinkers e) are also straight-chain or branched, linear or cyclic, aliphatic or
aromatic hydrocarbons which have at least two double bonds which, in the case of a li
phatic hydrocarbons, must not be conjugated, e.g. divinylbenzene, divinyltoluene, 1,7-
octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes
with molecular weights of from 200 to 20000.
Also suitable as crosslinkers e) are the acrylamides, methacrylamides and
N-allylamines of at least difunctional amines. Such amines are, for example,
1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane,
1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine.
Likewise suitable are the amides of allylamine and unsaturated carboxylic
acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at
least dibasic carboxylic acids as have been described above.
In addition, triallylamine and triallylmonoalkylammonium salts, e.g. triallylmethylammonium
chloride or methyl sulfate, are suitable as crosslinker e).
Also suitable are N-vinyl compounds of urea derivatives, at least difunctional amides,
cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartardiamide,
e.g. ,'-divinylethyleneurea or N,N'-divinylpropyleneurea.
Further suitable crosslinkers e) are divinyldioxane, tetraallylsilane or tetravinylsilane.
It is of course also possible to use mixtures of the abovementioned compounds e).
In one preferred embodiment of this invention, crosslinker e) is at least one of ethylene
glycol di(meth)acrylate, polyethylene glycol di(meth)acrylates, pentaerythritol triallyl
ether, methylenebisacrylamide, ,'-divinylethyleneurea, triallylamine and triallyl
monoalkylammonium salts.
In one preferred embodiment of this invention, crosslinker e) is pentaerythritol triallyl
ether.
Monomer f)
The polymers according to this invention comprise as polymerized units of from 0 to
30 % by weight of further monomers f) different from a) to e). In one embodiment of the
invention, the polymers comprise as polymerized units of from 1 to 20 % by weight of
such further monomers f). In still another embodiment of the invention, the polymers
comprise as polymerized units of from 2 to 10 % by weight of such further monomers
f)-
In one embodiment of the invention, at least one monomer f) is chosen from the group
consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
isopropyl (meth)acrylate, methyl ethacrylate, ethyl ethacrylate, n-propyl ethacrylate,
isopropyl ethacrylate, n-butyl ethacrylate, tert-butyl ethacrylate, isobutyl ethacrylate, nbutyl
(meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl
(meth)acrylate, 2-pentyl (meth)acrylate, 3-pentyl (meth)acrylate, isopentyl acrylate,
neopentyl acrylate, n-octyl (meth)acrylate, 1, 1 ,3,3-tetramethylbutyl (meth)acrylate,
ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-undecyl
(meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl
(meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl
(meth)acrylate, arrachinyl (meth)acrylate, behenyl (meth)acrylate, lignocerenyl
(meth)acrylate, cerotinyl (meth)acrylate, melissinyl (meth)acrylate, palmitoleinyl
(meth)acrylate, oleyl (meth)acrylate, linolyl (meth)acrylate, linolenyl (meth)acyrlate,
stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl acrylate, 4-t-butylcyclohexyl
acrylate, cyclohexyl (meth)acrylate, ureido (meth)acrylate, tetrahydrofurfuryl
(meth)acrylate and mixtures thereof.
One preferred embodiment of the invention is a polymer as described before, wherein
at least one monomer f) is chosen from esters of ,-ethylenically unsaturated monoand
dicarboxylic acids with d-Cs-alkanols.
Preferably, at least one monomer f) is chosen from C1-C6 alkyl (meth)acrylates, still
more preferred C1-C4 alkyl (meth)acrylates, e.g. from the group consisting of methyl
(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,
methyl ethacrylate, ethyl ethacrylate, n-propyl ethacrylate, isopropyl ethacrylate, n-butyl
ethacrylate, tert-butyl ethacrylate, isobutyl ethacrylate, n-butyl (meth)acrylate, tert-butyl
(meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate.
In one preferred embodiment of the invention, at least one monomer f) is chosen from
the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl
methacrylate, sec-butyl methacrylate and mixtures thereof.
In one particularly preferred embodiment of the invention, at least one monomer f) is or
comprises methyl methacrylate (MMA).
In another embodiment of the invention, at least one monomer f) is chosen from
compounds which are different from N-vinyl pyrrolidone and of the general formula VI
O
R— — NR2R3 (VI)
where R is a group of the formula CH2=CR4- where R4 = H or Ci-C4 -alkyl and R2 and
R3 are, independently of one another, H, alkyl, cycloalkyi, heterocycloalkyi, aryl or
hetaryl or R2 and R3 together with the nitrogen atom to which they are bonded are a 5-
to 8-membered nitrogen heterocycle or
R2 is a group of the formula CH2=CR4- and R and R3 are, independently of one
another, H, alkyl, cycloalkyi, heterocycloalkyi, aryl or hetaryl or R and R3 together with
the amide group to which they are bonded are a lactam having 5 to 8 ring atoms.
In one embodiment of the invention, preferred monomers f) are N-vinyllactams.
Suitable monomers f) are unsubstituted N-vinyllactams and N-vinyllactam derivatives,
which can, for example, have one or more Ci-C6 -alkyl substituents, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl etc. These include, for example,
N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-
2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-
methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam etc. and mixtures thereof.
In one embodiment of the invention, preferred monomers f) are N-vinylcaprolactam,
N-vinylformamide, acrylamide, methacrylamide, tert-butylacrylamide, N,Ndimethylacrylamide
or mixtures thereof.
In still another embodiment of the invention suitable monomers f) are the amides of
(meth)acrylic acid different from c). Such amides are, for example, Nmethyl(
meth)acrylamide, N-ethyl(meth)acrylamide, N-n-propyl(meth)acrylamide, N-ipropyl(
meth)acrylamide, N-(n-butyl)(meth)acrylamide, N-(sec-butyl)(meth)acrylamide,
N-(tert-butyl)methacrylamide, N-(n-pentyl)(meth)acrylamide, N-(nhexyl)(
meth)acrylamide, N-(n-heptyl)(meth)acrylamide, N-(n-octyl)(meth)acrylamide, N-
(tert-octyl)(meth)acrylamide N-(1 , 1 ,3,3-tetramethylbutyl)(meth)acrylamide, Nethylhexyl(
meth)acrylamide, N-(n-nonyl)(meth)acrylamide, N-(ndecyl)(
meth)acrylamide, N-(n-undecyl)(meth)acrylamide, N-tridecyl(meth)acrylamide,
N-myristyl(meth)acrylamide, N-pentadecyl(meth)acrylamide,
N-palmityl(meth)acrylamide, N-heptadecyl(meth)acrylamide, N-nonadecyl(meth)acrylamide,
N-arrachinyl(meth)acrylamide, N-behenyl(meth)acrylamide, N-lignocerenyl-
(meth)acrylamide, N-cerotinyl(meth)acrylamide, N-melissinyl(meth)acrylamide,
N-palmitoleinyl(meth)acrylamide, N-oleyl(meth)acrylamide, N-linolyl(meth)acrylamide,
N-linolenyl(meth)acrylamide, N-stearyl(meth)acrylamide, N-lauryl(meth)acrylamide.
In still another embodiment of the invention suitable monomers f) are 2-
hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide,
2-hydroxypropylacrylamide, 2-hydroxypropylmethacrylamide, 3-
hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide,
3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide,
4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide,
6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and
3-hydroxy-2-ethylhexylmethacrylamide.
In still another embodiment of the invention, at least one monomer f) is chosen from
vinyl acetate, vinyl propionate, vinyl butyrate, ethylene, propylene, isobutylene, butadi
ene, styrene, a-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene
chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
In still another embodiment of the invention, at least one monomer f) different from
acrylic acid is chosen from monomers with a free-radically polymerizable,
,-ethylenically unsaturated double bond and at least one anionogenic and/or anionic
group per molecule. Such monomers f) include monoethylenically unsaturated monoand
dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also
be used in the form of their salts or anhydrides. Examples thereof are methacrylic acid,
ethacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic
acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric
acid. Such monomers f) also include the half-esters of monoethylenically unsaturated
dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, e.g. of maleic acid,
such as monomethyl maleate. Such monomers f) also include monoethylenically un
saturated sulfonic acids and phosphonic acids, for example vinylsulfonic acid, allylsulfonic
acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl
methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic
acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic
acid, vinylphosphonic acid and allylphosphonic acid. Such monomers f) also include
the salts of the abovementioned acids, in particular the sodium, potassium and ammo
nium salts, and the salts with amines. Such monomers f) can be used as they are or as
mixtures with one another. The weight fractions given all refer to the acid form.
In one embodiment of the invention the component f ) is chosen from methacrylic acid,
ethacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride,
fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic
acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and mixtures
thereof.
In one preferred embodiment of the invention, component f ) is chosen from methacrylic
acid, ethacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride,
fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic
acid and mixtures thereof.
In one particulary preferred embodiment of the invention, component f) is or comprises
methacrylic acid.
In one embodiment of the invention, for the manufacture of the polymers, monomers d)
and f) are used as mixtures. Such mixtures of monomers d) and f) are for example mix
tures comprising Ci8 -(EO)25 methacrylate and methyl methacrylate (like e.g.
Plex®6877-0) or mixtures comprising Ci8 -(EO)25 methacrylate and methacrylic acid
(like e.g. Lutencryl ®250).
The following table shows exemplary compositional ranges of monomers a) to f) for
polymers according to this invention. The numbers are in % by weight with the proviso
that a) to f) add up to a total of 100 % by weight; a) is acrylic acid, b) is N-vinyl pyrrolidone,
c) is preferably N-vinyl imidazole, d) is preferably C16-C18 PEG-25 methacrylate,
i.e. monomer d) according to formula d1) wherein R8 is Methyl, X is Oxygen, k is about
25, I is zero, R9 is a mixture of C16 alkyl and C18 alkyl; e) is preferably pentaerythritol
triallyl ether (PETAE); and f) is preferably methyl methacrylate and/or methacrylic acid.
One embodiment of the invention are polymers comprising as polymerized units
a) 30 to 70 % by weight of acrylic acid,
b) 25 to 60 % by weight of N-vinyl pyrrolidone,
c) 2 to 10 % by weight of monomer c), preferably N-vinyl imidazole,
d) 1 to 9 % by weight of monomer d), preferably C16-C18 PEG-25 methacrylate,
e) 0.1 to 1.5 % by weight of at least one crosslinking agent e), preferably PETAE,
f) 1 to 15 % by weight of further monomers different from a) to e),
the total of a) to f) adding up to 100 % by weight.
Another embodiment of the invention are polymers comprising as polymerized units
a) 30 to 50 % by weight, preferably 35 to 45 % by weight of acrylic acid,
b) 30 to 50 % by weight, preferably 35 to 45 % by weight of N-vinyl pyrrolidone,
c) 2 to 8 % by weight of monomer c), preferably N-vinyl imidazole,
d) 3 to 9 % by weight of monomer d), preferably C16-C18 PEG-25 methacrylate,
e) 0.5 to 1.5 % by weight of at least one crosslinking agent e), preferably PETAE,
f) 2 to 10 % by weight, preferably 4 to 8 % by weight of further monomers different from
a) to e), preferably methacrylic acid and/or methylmethacrylate, the total of a) to f) adding
up to 100 % by weight.
Another embodiment of the invention are polymers comprising as polymerized units
a) 35 to 45 % by weight of acrylic acid,
b) 40 to 55 % by weight of N-vinyl pyrrolidone,
c) 2 to 8 % by weight of monomer c), preferably N-vinyl imidazole,
d) 2 to 6 % by weight of monomer d), preferably C16-C18 PEG-25 methacrylate,
e) 0.5 to 1.5 % by weight of at least one crosslinking agent e), preferably PETAE,
f) 4 to 15 % by weight, preferably 4 to 10 % by weight of methylmethacrylate,
the total of a) to f) adding up to 100 % by weight.
Another embodiment of the invention are polymers comprising as polymerized units
a) 65 to 75 % by weight of acrylic acid,
b) 10 to 25 % by weight of N-vinyl pyrrolidone,
c) 0.5 to 2 % by weight of monomer c), preferably N-vinyl imidazole,
d) 2 to 6 % by weight of monomer d), preferably C16-C18 PEG-25 methacrylate,
e) 0.5 to 1.5 % by weight of at least one crosslinking agent e), preferably PETAE,
f) 2 to 8 % by weight, preferably 3 to 6 % by weight of methacrylic acid and 0.2 to 1.0 %
by weight of methylmethacrylate,
the total of a) to f) adding up to 100 % by weight.
Another embodiment of the invention are polymers comprising as polymerized units
a) 70 to 80 % by weight of acrylic acid,
b) 10 to 18 % by weight of N-vinyl pyrrolidone,
c) 0.5 to 3 % by weight of monomer c), preferably N-vinyl imidazole,
d) 2 to 6 % by weight of monomer d), preferably C16-C18 PEG-25 methacrylate,
e) 0.5 to 1.5 % by weight of at least one crosslinking agent e), preferably PETAE,
f) 2 to 6 % by weight, preferably 3 to 6 % by weight of methacrylic acid and 0.2 to 1.0 %
by weight of methylmethacrylate,
the total of a) to f) adding up to 100 % by weight.
Precipitation Polymerization
The polymers according to the invention are manufactured by the method of precipita
tion polymerization.
The invention thus further provides a method for manufacturing the polymers according
to the invention wherein the polymerization is a precipitation polymerization.
In a specific embodiment of the precipitation polymerization use is made of at least two
free-radical initiators whose decomposition temperatures and/or half-lives thereof at a
certain polymerization temperature are different from one another. As a result, copoly
mers with particularly low residual monomer contents can be achieved. This is the
case, particularly if the initiator that decomposes at the higher temperature is added
before the polymer has finished precipitating, preferably before the polymer has started
precipitating.
During precipitation polymerization the monomers are soluble in the reaction medium
which comprises the monomers and the solvent but not the resulting polymer. The re
sulting polymer becomes insoluble under such polymerization conditions and precipi
tates. Thereby it is possible to obtain copolymers with higher molecular weights com
pared to other polymerization processes, e.g. through solution polymerization. Such
copolymers having relatively high molecular weights are particularly advantageous as
rheology modifiers, in particular as thickeners.
The precipitation polymerization preferably takes place in a solvent, in which each of
the monomers used is soluble (at 20°C and 1 bar) in an amount of at least 10% by
weight to give a solution visibly clear to the human eye.
The precipitation polymerization takes place, for example, in esters such as ethyl ace
tate or butyl acetate and/or hydrocarbons such as cyclohexane or n-heptane as so l
vents. In one embodiment of the invention mixtures of ethyl acetate and cyclohexane
are used as solvent.
The resulting polymer particles precipitate from the reaction solution and may be isolated
by known methods such as filtration at reduced pressure.
The polymerization temperatures are preferably in a range from about 30 to 120°C,
particularly preferably from 40 to 100°C.
Suitable Initiators for the free-radical polymerization are peroxo and/or azo compounds
customary for this purpose, for example alkali metal or ammonium peroxydisulfates, diacetyl
peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl
perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleate,
cumene hydroperoxide, diisopropyl peroxydicarbamate, bis(o-toluoyl) peroxide,
didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate,
tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, 2,2'-Azobis(2.4-
dimethyl valeronitrile), Azobis(2-amidinopropane) dihydrochloride, 2-2'-Azobis(2-
methylbutyronitrile) (Wako®V65), tert.butyl peroctoate (CAS No 13467-82-8), 2,5-
Dimethyl-2,5-bis(t-butylperoxy)hexane (Trigonox ®10 1) .
Also suitable are initiator mixtures or redox initiator systems, such as, for example,
ascorbic acid/iron(ll) sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium d i
sunite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate, H202 /Cu(l).
To produce polymers with minimized residual monomer contents, the first polymeriza
tion (main polymerization) may be followed by an afterpolymerization step. For such
afterpolymerization the same or a different initiator system as for the main polymeriza
tion may be used. Preferably the temperature of the afterpolymerization step is equal
to, preferably higher than the main polymerization temperature. The reaction tempera
ture during the main polymerization is preferably at most 100°C and during the after
polymerization preferably at most and 130°C.
In a specific embodiment at least two free radical initiators which permit an essentially
independent initiation in at least two phases are used for the preparation of the poly
mers according to the invention. Thereby polymers with particularly low residual
monomer contents can be achieved.
US 2008/0199416 A 1, [0494] to [0508], which is herewith incorporated by reference,
gives a detailed description of such a kind of process.
After polymerization the precipitated polymer is isolated from the reaction mixture.
Therefore any method known to the skilled person can be used. Such methods are
filtration, centrifugation, evaporation of the solvent or combinations of these methods.
The polymers can be further purified by conventional washing steps with the same so l
vents that have been used for the polymerization itself.
Resulting dry polymer powders can advantageously be converted to an aqueous solution
or dispersion by dissolution or redispersion, respectively, in water. Pulverulent co
polymers have the advantage of better storability and easier transportability and usually
exhibit a lower propensity for microbial attack.
The acid groups of the polymers can be partially or completely neutralized with a base.
Bases which can be used for the neutralization of the polymers are alkali metal bases
such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate,
sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate,
ammonium bicarbonate, ammonium carbonate, and alkaline earth metal bases, such
as calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium carbonate
and also amines. Suitable amines are, for example, Ci-C6 -alkylamines, preferably npropylamine
and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine,
trialkylamines, preferably triethylamine and triisopropylamine. Preference
is given to amino alcohols, e.g. trialkanolamines, such as triethanolamine, alkyldialkanolamines,
such as methyl- or ethyldiethanolamine and dialkylalkanolamines,
such as dimethylethanolamine, and also 2-amino-2-methyl-1-propanol. Particularly for
use in hair treatment compositions, 2-amino-2-methyl-1-propanol, 2-amino-2-
ethylpropane-1 ,3-diol, diethylaminopropylamine and triisopropanolamine have proven
particularly useful for the neutralization of the polymers comprising acid groups. The
neutralization of the acid groups can also be carried out with the aid of mixtures of two
or more bases, e.g. mixtures of sodium hydroxide solution and triisopropanolamine.
Depending on the intended used, the neutralization can take place partially or com
pletely.
In one preferred embodiment of the invention the precipitation polymerization is carried
out in the presence of at least one surfactant. Preferably, this surfactant has an HLB
value of less than or equal to 10.
Using the HLB-value (according to W.C. Griffin, J. Soc. Cosmetic Chem. 1 ( 1949) 3 11),
emulsifiers can be classified according to the ratio of hydrophilic groups to lipophilic
groups (HLB = hydrophilic-lipophilic balance).
Suitable surfactants with an HLB value of less than or equal to 10 are described, for
example, in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika [Funda
mentals and Formulations of Cosmetics], 2nd edition, Verlag Huthig, Heidelberg, pp.
395 - 397, to which reference is made here in its entirety.
The determination of the HLB value of emulsifiers is known to the person skilled in the
art and is described, for example, on p. 394 of the abovementioned literature reference.
Further suitable surfactants with an HLB value of less than or equal to 10 are listed, for
example, in US 4375533, column 7, II. 26 - 60, to which reference is made here in its
entirety. The use of surfactants in the precipitation polymerization of crosslinked polyacrylic
acid is already described in US 4420596 and US 4375533.
The invention thus also provides a method as described above where the precipitation
polymerization is carried out in the presence of at least one surfactant which is chosen
from linear block copolymers with a hydrophobic structural unit with a length of more
than 5 nm (calculated by the law of cosines), which are defined by the following for
mula:
in which
A is a hydrophilic structural unit which has a solubility in water at 25°C of 1% by weight
or more, has a molar mass Mw of from 200 to 50 000, and is selected such that it is
bonded covalently to B;
B is a hydrophobic structural unit which has a molar mass Mw of from 300 to 60 000,
has a solubility in water at 25°C of less than 1% by weight and can be covalently
bonded to A;
C and D are end groups which may be A or B and the same group or different groups;
w is 0 or 1;
x is an integer greater than or equal to 1,
y is 0 or 1, and
z is 0 or 1.
The invention further provides a method as described above where the precipitation
polymerization is carried out in the presence of at least one surfactant chosen from
random comb copolymers which are defined by the following formula:
in which
R and R2 are end groups and may be identical or different from one another
and are different from Z and Q,
Z is a hydrophobic structural unit which has a solubility in water of 25°C of less than 1%
by weight,
Q is a hydrophilic structural unit which has a solubility in water of 25°C of more than 1%
by weight,
and
m and n are integers greater than or equal to 1 and are selected such that the molar
mass Mw is from 100 to 250 000.
In one preferred embodiment of the invention the surfactants are selected from 12-
hydroxystearic acid block copolymers, further preferably 12-hydroxystearic acid block
copolymers with polyethylene oxide. The 12-hydroxystearic acid block copolymers are
particularly preferably ABA block copolymers.
1) Hypermer® B239: block copolymer of a polyhydroxy fatty acid (PFA) and polyethyl
ene oxide (PEO) with Mw of about 3500;
2) Hypermer® B246: block copolymer of a polyhydroxy fatty acid (PFA) and polyethyl
ene oxide (PEO) with Mw of about 7500.
3) Hypermer ® B261 : block copolymer of a polyhydroxy fatty acid (PFA) and polyethyl
ene oxide (PEO) with Mw of about 9600.
4) Hypermer ® 2234: nonionic polymeric surface-active compound;
5) Hypermer ® LP6: polymeric fatty acid ester with Mw of about 4300.
6) Hypermer ® IL2296: nonionic polymeric surface-active compound;
7) Hypermer ® A-109 block copolymer of a fatty acid or of a long-chain alkylene radical
with ethylene oxide.
8) Hypermer ® A-409 block copolymer of a fatty acid or of a long-chain alkylene radical
with ethylene oxide.
9) Pecosil ® PS-100 dimethicone copolyol phosphate polymer with 5-12 mol of ethylene
oxide per mole of the hydrophilic unit.
10 ) Pecosil ® WDS-100 dimethicone copolyol phosphate polymer with 5-12 mol of pro
pylene oxide per mole of the hydrophilic unit.
Useful surfactants are disclosed in EP 584771 B 1 , page 23, lines 2 to 37, which is
hereby incorporated by reference.
In another embodiment of the invention the surfactant is selected from the group con
sisting of
- copolymers of polydimethylsiloxanes and organic glycols,
- substances with the INCI name dimethicone PEG-7 phosphate,
- polyesters comprising polyethylene glycol,
- polyoxyethylene-glycerol-fatty-acid esters,
- polyamide waxes,
- natural waxes and
- mixtures thereof.
Other surfactants are copolymers of polydimethylsiloxanes and organic glycols like e.g.
substances with the INCI name PEG/PPG-25/25 dimethicone (e.g. Belsil®DMC 6031)
and dimethicone copolyol acetate (e.g. Belsil®DMC 6032).
Another suitable commercially available dimethicone PEG-7 phosphate ( INCI) is e.g.
Pecosil ®PS-100.
Other suitable commercially available dimethicones are aminoalkyl subsituted dimethicones
like e.g. Methoxy PEG/PPG-7/3 Aminopropyl Dimethicone (Abil®Soft AF 100 by
Evonik). Aminoalkyl subsituted surfactants enable higher solid contents during the pre
cipitation polymerization compared to the use of non aminated surfactants.
Commercially available polyesters comprising polyethylene glycol that may be used as sur
factants in the precipitation polymerization are block copolymers of the Hypermer ® brand,
in particular the grades B239, B246, B261 , 2234, LP6, A-109, A-409 (described in
EP 584771 B 1, pagelO, lines 25-42).
Other surfactants in the presence of which the monomers are polymerized to yield the polymers
of this invention are mixtures of different ethoxilated long chain fatty alcohols, like e.g.
Leophen ®RW ECO.
Commercially available polyoxyethylene-glycerol-fatty-acid esters also suitable as surfac
tants are e.g. polyglyceryl-2 dipolyhydroxystearates ( INCI) such as Dehymuls ®PGPH (Cognis).
Other suitable surfactants are compounds with the INCI names PEG-7 Hydrogenated Cas
tor Oil, such as Arlacel ®989, Cremophor ®W07 ( BASF) or Dehymuls ®HRE 7 (Cognis),
PEG-2 Hydrogenated Castor Oil such as Arlacel ®582, sorbitan monooleate/propylglyceryl
4/3-ricinoleate, such as Arlacel ®1689 (Croda), sorbitan stearate and sucrose cocoate such
as, for example, Arlartone ®2121 (Croda), sorbeth-20 beeswax such as, for example, Atlas
®G-1726 (Croda).
Another suitable surfactant is a polyamide wax like e.g. Kahl Wax 6635 (Kahl&Co).
Other suitable commercially available natural waxes are e.g. mixtures of fatty acid es
ters, fatty acid and fatty alcohol, such as, for example, beeswax, berry wax, rice wax
(Kahl&Co). Suitable beeswaxes are in particular those with the CAS numbers 8006-40-
4 (white) or 8012-89-3. Suitable beeswaxes bear the INCI (EU) names Cera Alba, syn
thetic beeswax, PEG-7 dimethicone beeswax. Particularly suitable beeswaxes are
those with the INCI EU name Cera Alba.
Suitable berry waxes are e.g. those with the INCI name Rhus Verniciflua Peel Wax
(Berry Wax 6290 (Kahl & Co) or Botaniwax ®OT(Botanigenics, Inc)).
Suitable rice waxes are in particular those with CAS number 8016-60-2 or the INCI
name Oryza Sativa (rice) bran wax. Such rice waxes are available commercially as
Cerewax ® (Chemyunion Quimica LTDA), ESP®Rice Bran Wax (Earth Supplied
Products, LLC), Florabeads ®RBW(Floratech Americas), Naturebead ®R20 (Micro
Powders, Inc. Personal Care Division), Oryza Soft®"COS" (Cosmetochem International
Ltd.), ORYZA ® Wax (lchimaru Pharcos Company, Ltd.), Ricebran Wax SP 8000 (Strahl
& Pitsch, Inc.), Rice Wax No.1(Tri-K Industries), Rice Wax 281 1 (Kahl).
The amount of surfactant present during the precipitation polymerization is in the range
from 0.001 to 50% by weight, preferably from 0.01 to 20% by weight and particularly
preferably in the range from 0.1 to 10% by weight, based on the total amount of 100%
by weight of the components a) to f).
On account of their thickening effect, the polymers obtainable by the method according
to the invention can be used as the sole gel former in cosmetic preparations. Moreover,
they are also suitable for use in combination with customary gel formers.
The polymers according to the invention can be used, in particular as thickeners, in
aqueous preparations in the sectors of household, personal care, building industry,
textiles, for paper coating slips, pigment printing pastes, aqueous colors, leathertreatment
compositions, cosmetic formulations, pharmaceutical products and agrochemicals.
Another embodiment of this invention is a method for modifying the viscosity of aque
ous compositions, wherein said method comprises adding a polymer according to this
invention to said aqueous compositions.
Furthermore, the polymers of this invention are easy to handle, allow for use of con
tinuous production processes with use of in-line static mixers, can be processed with
membrane pumps and, when diluted, with turbine mixers and high speed propellers,
are able to formulate clear products, can be used with electrolytes, support the stabilization
of hydrophobic (low solubility) components, are compatible with nonionic, ani
onic, zwitterionic and some cationic surfactants, are able to stabilize suspensions, are
mild, soft, non-greasy, non-sticky, stable in pH 5.5 to 12 formulations, thicken and sta
bilize hydrogen peroxide, and allow a flexible choice of the preservative system.
Another embodiment of this invention are cosmetic preparations, which comprise the
polymers according to the invention.
Non-limiting examples for cosmetic preparations where the polymers of this inventions
can be advantageously used are anti-dandruff shampoos, bath foams, curl activators,
depilatories, emulsifier free formulations, foaming facial cleansers, hair styling gels,
liquid soaps, lotions, moisturizing creams, shampoos, shower gels, skin masks, water
less hand cleaners, and wave sets.
Examples
The invention is illustrated in more detail by reference to the following nonlimiting
examples.
Abbreviations:
VP N-Vinyl pyrrolidone
MAA Methacrylic acid
AA Acrylic acid
MA methacrylate
MMA methyl methacrylate
VI N-Vinyl imidazole
EAc Ethyl acetate
CH Cyclohexane
PETAE Pentaerythritol triallyl ether
C 6-18-Alkyl-PEG-MA Methacrylic acid ester of a C 6-Ci 8-fatty alcohol alkoxylated
with 25 moles of ethylene oxide
Plex®6877-0: Ci 6 -i8 -Alkyl-PEGnoo - methacrylate in methyl methacrylate [25:75 w:w]
Lutencryl®250: Ci 6 -i8 -Alkyl-PEGnoo - methacrylate in methacrylic acid (MAS) [50:50
w:w]
LUMA: Ci6-i8-Alkyl-PEGi ioo - methacrylate
I.) Preparation of polymers
Preferably, the polymers of this invention are manufactured by precipitation polymeriza
tion.
Example 67:
Copolymer of AA / VP / VI / C 6- 8-Alkyl-PEG-MA / PETAE / MAA (40/37/6/8/1/8 w/w)
Initial charge:
1020 g ethyl acetate (EAc)
6 g Belsil® DMC 6031
150 g ethyl acetate
240 g acrylic acid
222 g N-vinyl pyrrolidone
36 g N-vinyl imidazole
96 g Lutencryl®250
8 g pentaerythritol triallyl ether
300 g ethyl acetate
3.31 g tert-butyl peroctoate
0.30 g Wako® V 50
Feed 3: 900 g ethyl acetate
A stirred reaction vessel was filled with initial charge, kept under nitrogen atmosphere
and the initial charge was heated to 70°C. Feed 1 was then added continuously during
3 hours and Feed 2 was added continuously during 5 hours. After completion of Feed
1, Feed 3 was added continuously during 1.5 hours. After completion of Feed 2, the
reaction mixture was heated to 75°C and kept at 75°C for another 3 hours before it was
heated to 100°C and kept at 100°C for another 4 hours.
Polymers of examples 1 to 5 1 and 62 to 97 were prepared in an analogous manner.
For the preparation of the polymers of example 52 to 6 1, a 1: 1 w/w mixture of ethyl
acetate and cyclohexane has been used instead of ethyl acetate.
All monomer amounts given in the following table are in weight-%.
Plex® Lutencryl® Sur¬
Polymer No AA VP V I PETAE
6877-0 250 factant
36 40 48.3 3 8 0 0.7 1%1)
37 40 48.2 3 8 0 0.8 1%1)
38 40 48.1 3 8 0 0.9 1%1)
39 43 45 3 8 0 1.0 1%1)
40 40 45.2 6 8 0 0.8 1%1)
4 1 40 48.2 3 8 0 0.8 1%1)
42 40 46.2 3 10 0 0.8 1%1)
43 40 44.2 3 12 0 0.8 1%1)
44 50 34 3 12 0 1 1%1)
45 50 34 3 12 0 1 1%1)
46 45 45 3 6 0 1 1%1)
47 40 48.3 3 8 0 0.7 1%1)
48 40 48.2 3 8 0 0.8 1%1)
49 40 48.1 3 8 0 0.9 1%1)
50 40 45 6 0 8 1 1%1)
5 1 40 44.9 6 0 8 1. 1 1%1)
52 60 30.5 1 0 8 0.50 0
Plex® Lutencryl® Sur¬
Polymer No AA VP V I PETAE
6877-0 250 factant
53 65 25.5 1 0 8 0.50 0
54 70 20.5 1 0 8 0.50 0
55 70 16.5 1 0 12 0.50 0
56 70 12.5 1 0 16 0.50 0
57 73.3 17 0 8 0.7 1.5% >
58 56.5 30 3 10 0 0.5 1% >
59 56.5 30 3 10 0 0.5 2% >
60 56.5 30 3 10 0 0.5 1% >
6 1 54.5 30 5 10 0 0.5 1% >
62 54.5 30 3 12 0 0.5 1% >
63 50 36.4 3 10 0 0.6 1% >
64 40 48.4 3 8 0 0.6 1% >
65 30 58.4 3 6 0 0.6 1% >
66 40 40 9.4 10 0 0.6 1% >
67 40 37 6 0 16 1.0 1% >
68 45 45 2 0 8 0.5*) 1% >
69 45 45 2 0 8 0.6*) 1% >
70 45 45 2 0 8 0.5*) 1%5>
7 1 47 47 2 0 4 0.6*) 1% >
72 58 36 2 0 4 0.5*) 1% >
73 60 30 2 0 8 0.5*) 1% >
74 60 30 2 0 8 0.5*) 1% >
75 65 22 2 0 11 0.5*) 1% >
76 66 22 2 0 10 0.5*) 1% >
77 70 22 2 0 6 0.5*) 1% >
78 70 22 2 0 6 0.4*) 1% >
79 70 20 2 0 8 0.5*) 0
80 73 17 2 0 8 0.5*) 1% >
8 1 73 17 2 0 8 0.5*) 1%5>
82 74 17 1 0 8 0.5*) 1% >
Plex® Lutencryl® Sur¬
Polymer No AA VP VI PETAE
6877-0 250 factant
83 74 17 0 8 04*) 1% >
84 74 17 0 8 0.3*) 1% >
85 74 17 1 0 8 0.5*) 1%5>
86 74 2 1 0 4 0.5*) 1% >
87 78 17 0 4 0.5*) 1% >
88 78 10 1 0 1 1 0.5*) 1% >
89 79 12 0 8 0.5*) 1% >
90 79 12 0 8 0.5*) 1%5>
9 1 80 1 1 1 0 8 0.5*) 1% >
92 80 1 1 0 8 0.4*) 1% >
93 80 1 1 0 8 0.3*) 1%5>
94 80 15 1 0 4 0.5*) 1% >
95 83 12 0 4 0.5*) 1% >
96 84 12 0 3 0.5*) 1% >
97 85 10 0 4 0.5*) 1% >
: Belsil® DMC 6031 was used as surfactant ; amount given in weight-% with re
spect to sum of amount of monomers AA, VP, VI, monomer d), f) and PETAE which
add up to 100 weight-%;
2 : Plex®6877-0 was used as monomers d) + f);
: Lutencryl®250 was used as monomers d) + f);
4 : Hypermer®B246 was used as surfactant ; amount given in weight-% with respect
to sum of amount of monomers AA, VP, VI, monomer d), f) and PETAE which add
up to 100 weight-%;
: Abil®Soft AF 100 was used as surfactant; amount given in weight-% with respect
to sum of amount of monomers AA, VP, VI, monomer d), f) and PETAE which add
up to 100 weight-%;
* ) amount of PETAE in weight-% with respect to the total amount of all other
monomers being 100 % by weight.
II.) Application of polymers
In the following, the term "Polymer selected from No. 1 to 97" means any of the
Polymers No 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 2 1, 22,
23, 24, 25, 26, 27, 28, 29, 30, 3 1, 32, 33, 34, 35, 36, 37, 38, 39, 40, 4 1, 42, 43, 44, 45,
46, 47, 48, 49, 50, 5 1, 52, 53, 54, 55, 56, 57, 58, 59, 60, 6 1, 62, 63, 64, 65, 66, 67, 68,
69, 70, 7 1, 72, 73, 74, 75, 76, 77, 78, 79, 80, 8 1, 82, 83, 84, 85, 86, 87, 88, 89, 90, 9 1,
92, 93, 94, 95, 96, 97.
Hair gels containing a nonionic hair-setting agent:
CTFA % by wt.
Phase 1:
Polymer selected from No. 1 to 97 0.5
Water, dist. 49.5
Further additive: preservative, e.g. Euxyl® K100, perfume, etc.
with triethanolamine (50% strength solution) adjust to pH between 6.7 and 7.4
Phase 2:
Luviskol® K90 Polyvinylpyrrolidone 3.0
Water, dist. ad 1
Further additives: perfume, emulsifier, UV-absorber, etc.
Preparation:
Phase 1 is weighed and homogenized with stirring at a temperature in the range from
20 to 50°C. After about 1 to 3 hours, a milky dispersion forms. Triethanolamine is
added with stirring. After about 2 hours, a (virtually) homogeneous, high-viscosity gel is
formed. Phase 2 is then stirred slowly into phase 1. The gel is stirred at room
temperature for a further hour. This produces a stable, nearly clear to clear gel.
Hair gels containing polv(vinylpyrrolidone/vinyl acetate)
CTFA % by wt.
Phase 1:
Polymer selected from No. 1 to 97 0.5
Water, dist. 49.5
Further additive: preservative, e.g. Euxyl® K100, perfume etc.
with triethanolamine (50% strength solution) adjust to pH between 6.7 - 7.4.
Phase 2:
Luviskol® VA64 Poly(vinylpyrrol- 4.5
idone/vinyl acetate)
Water, dist. ad 100
Further additives: perfume, emulsifier, UV-absorber, etc.
Preparation:
Phase 1 is weighed and homogenized with stirring at a temperature in the range from
20 to 50°C. After about 3 hours, a milky dispersion forms. Triethanolamine is added
with stirring. After about 2 hours, a (virtually) homogeneous, high-viscosity gel is
formed. Phase 2 is then stirred slowly into phase 1. The gel is stirred at room
temperature for a further hour. This produces a stable, nearly clear to clear gel.
Hair gels containing a cationic hair polymer
CTFA % by wt.
Phase 1:
Polymer selected from No. 1 to 97 1.0
Water, dist. 49
Further additive: preservative, e.g. Euxyl® K100, perfume, etc
with triethanolamine (50% strength solution) adjust to pH between 6.7-7.2
Phase 2:
Luviskol® K90 Polyvinylpyrrolidone 1.5
Luviquat® Supreme (BASF AG) Polyquaternium-68 0.5
Water, dist. ad 100
Further additives: perfume, emulsifier, UV-absorber, etc.
Preparation:
Phase 1 is weighed and homogenized with stirring at a temperature in the range from
20 to 50°C. After about 3 hours, a milky dispersion forms. Triethanolamine is added
with stirring. After about 2 hours, a (virtually) homogeneous, high-viscosity gel is
formed. Phase 2 is then stirred slowly into phase 1. The gel is stirred at room
temperature for a further hour. This produces a stable gel.
Shampoo (without the addition of salt)
CTFA % by wt.
Phase 1:
Polymer selected from No. 1 to 97 1.7
Water 47.5
with triethanolamine (50% strength) adjust to pH 6 to 7
Phase 2:
Texapon® NSO 28% strength Sodium Laureth Sulfate/ 50.0
Henkel
Comperlan® KD Coamide DEA / Henkel 1.0
Further additive: perfume, preservative, etc.
Preparation:
Weigh in and, with stirring, dissolve phases 1 and 2 separately and mix. Slowly stir
phase 2 into phase 1.
Claims
1 Polymer comprising as polymerized units
a) 25 to 85 % by weight of acrylic acid,
b) 10 to 60 % by weight of N-vinyl pyrrolidone,
c) 0.5 to 10 % by weight of at least one cationic monomer,
d) 0.5 to 10 % by weight of at least one of compounds d1) or d2)
8 O
(CH 2 C H 2O ) k (CH 2 CH(CH 3 )O),
(d1 )
H 2 C=CH C H 2 O (CH 2 C H 2O ) k (CH 2 C H (CH3)O), R
(d2)
wherein
the order of the alkylene oxide units is arbitrary,
k and I, independently of one another, are an integer from 0 to 1000,
where the sum of k and I is at least 5,
R is hydrogen or Ci-C4 -alkyl,
R is Cs-Cso -alkyl, Cs-Cso -alkenyl or C8-C30 alkylaryl, and
X is O or a group of the formula NR 0 , in which R 0 is H, alkyl, alkenyl,
cycloalkyl, heterocycloalkyl, aryl or hetaryl,
e) 0.01 to 2 % by weight of at least one crosslinking agent,
f) 0 to 30 % by weight of further monomers different from a) to e),
the total of a) to f) adding up to 100 % by weight.
2 Polymer according to claim 1, wherein at least one cationic monomer c) is
chosen from vinylimidazole compounds of the general formula (II)
(II)
in which R5 to R7, independently of one another, are hydrogen, Ci-C4 -alkyl or
phenyl.
Polymer according to claim 2, wherein at least one cationic monomer c) is Nvinyl
imidazole.
Polymer according to one of claims 1 to 3, wherein at least one monomer f) is
chosen from methacrylic acid, esters of ,-ethylenically unsaturated monoand
dicarboxylic acids with d -Cs-alkanols.
Polymer according to claim 4, wherein at least one monomer f) is chosen
from Ci-C6 -(meth)acrylates.
Polymer according to one of claims 1 to 5, wherein at least one compound
d ) is chosen from polyether (meth)acrylates terminated with C8-C22 -alkyl
groups.
Polymer according to one of claims 1 to 6, wherein the molar ratio of com
pounds a) to c) is at least 4:1 .
Polymer according to one of claims 1 to 7, comprising as polymerized units
a) 65 to 75 % by weight of acrylic acid,
b) 10 to 25 % by weight of N-vinyl pyrrolidone,
c) 0.5 to 2 % by weight of N-vinyl imidazole,
d) 2 to 6 % by weight of Ci6-Cie PEG-25 methacrylate,
e) 0.5 to 1.5 % by weight of at least one crosslinking agent,
f) 2 to 8 % by weight of methacrylic acid and 0.2 to 1.0 % by weight of methylmethacrylate,
the total of a) to f) adding up to 100 % by weight.
9. Cosmetic composition comprising a polymer according to one of claims 1 to
8.
10. Method for modifying the viscosity of aqueous compositions, wherein said
method comprises adding a polymer according to one of claims 1 to 8 to said
aqueous compositions.