Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
PF 72097 CA 02836849 2013-11-20
Branched polyesters with sulfonate groups
Description
The present invention relates to branched polyesters with sulfonate groups and
mixtures
comprising branched polyesters with sulfonate groups. The invention further
provides a method
for producing such branched polyesters. Furthermore, the invention relates to
the use of these
branched polyesters as soil release polymers and graying inhibitors, for
example in the cleaning
of textiles, as textile auxiliaries and cleaners for hard surfaces.
Further embodiments of the present invention can be found in the claims, the
description and
the examples. It goes without saying that the features of the subject matter
according to the
invention that have been specified above and are still to be explained below
can be used not
only in the combination specifically stated in each case, but also in other
combinations, without
departing from the scope of the invention. In particular, also those
embodiments of the present
invention in which all of the features of the subject matter according to the
invention have the
preferred or very preferred meanings are preferred or very preferred.
Branched copolyesters comprising sulfonate groups which are soluble or can be
dispersed in
water are known from DE 26 21 653 A1. These branched copolyesters are
suitable, according
to DE 26 21 653 A1, as leveling auxiliaries in polyester dyeing, in particular
for rapid dyeing
methods, as hair-setting compositions, as sizes, as water-soluble adhesives
and as additive for
adhesives, and also as modifiers for melamine resins or other aminoplastic
resins.
DE 26 33 418 A1 describes hair treatment compositions with a content of water-
soluble or
-dispersible branched copolyesters comprising sulfonate groups.
DE 26 37 926 A1 describes water-soluble or -dispersible and branched
copolyesters comprising
sulfonate groups with an application spectrum comparable to DE 26 21 653 A1.
US 5,281,630 describes a prepolymer based on a terephthalic polymer, glycol
and oxyalkylated
polyol, which is reacted with (1,8-unsaturated dicarboxylic acids and is then
sulfonated.
Alemdar et al. describe in Polymer 51 (2010), pp. 5044-5050, the production of
unsaturated
polyesters using boric acid as catalyst and sulfonated derivatives of the
unsaturated polyesters
as biodegradable polymeric surface-active substances.
DE 39 05 915 A1 relates to a coating composition comprising addition polymers,
crosslinking
agents and an acid catalyst. Hydroxyl-comprising succinic acid diestersulfonic
acids and
succinic acid polyestersulfonic acids are described as acid catalysts.
Simple sulfosuccinates, for example mono- or dialkyl sulfosuccinates or
sulfosuccinamides,
have already been well-known to the person skilled in the art from the prior
art since 1930.
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These sulfosuccinates are used, for example, in cleaning compositions,
pharmaceuticals,
adhesives or coatings. However, polymeric sulfosuccinates are barely used.
An overview of the fields of use of sulfosuccinates can be found, for example,
in Anionic
Surfactants: Organic Chemistry, edited by H. W. Stache, Marcel Dekker, New
York, 1996:
Chapter 9: Sulfosuccinates by A. Domsch, and B. Irrgang.
Soil release polymers have been the subject of intense development work for
many years.
Originally developed as textile auxiliaries for the finishing of synthetic
fibers, in particular
polyester fibers, they are nowadays also used as so-called washing auxiliaries
in detergents
and cleaners for household laundry. Common names for soil-releasing compounds
of this type
are "Soil Release Polymers" or "Soil Repellents", because they impart soil-
repelling properties
to the treated surfaces.
The majority of the soil release polymers are polyesters based on terephthalic
acid,
polyalkylene glycols and monomeric glycols.
EP 1 035 194 A2 relates to the use of soil release comb polymers in detergents
and cleaners.
Also known from EP 1 035 194 A2 (paragraph [0005]) are soil release
polyesters, which can
comprise anionic groups such as, for example, sulfonate groups.
The redeposition of dirt on textile fibers during the washing process is a
constant challenge for
the users. Consequently, additives which help to reduce this redeposition are
in-demand
additives, for example for detergents. In the past, high-performance additives
were developed
for powder detergents, but these no longer fully comply with modern
requirements (e.g.
formulatability in liquid detergents).
It was therefore the object of the invention to provide substances which can
be used for
cleaning purposes, in particular as additive to cleaner formulations for the
treatment of textiles
and household laundry. The object of the invention was also to provide
polymeric effect
substances by means of a technically simple and cost-effective method which
have a large
number of carboxyl groups and/or sulfonic acid groups and consist of monomers
of low toxicity.
It was a further object of the invention to provide substances which can
easily be incorporated
into formulations for cleaning purposes in their various presentation forms.
As is evident from the disclosure of the present invention, these and other
objects are achieved
by the various embodiments of the branched polyesters with sulfonate groups
according to the
invention, which are obtainable by
a. the reaction of the components A, B, optionally C and optionally D to give
branched
polyesters, where
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i. the component A is selected from the group of a,p-olefinically unsaturated
dicarboxylic acids (A2), and
ii. the component B is selected from the group of tri- or higher-functional
alcohols (By),
iii. the optional component C is selected from the group of difunctional
alcohols
(B2) or the difunctional carboxylic acids (C2) without a,p-olefinically
unsaturated bonds,
iv. the optional component D is selected from fatty acids or fatty alcohols,
b. and the subsequent reaction of the branched polyesters obtained in (a.)
with hydrogen
sulfite, where the molar amount of hydrogen sulfite is at most 95 mol%, based
on the
amount of a,p-olefinically unsaturated dicarboxylic acid (A2).
Surprisingly, it has inter alia been found that these branched polyesters with
sulfonate groups
reduce the redeposition of dirt and the graying of polyester fibers.
In the reaction of the components A, B, optionally C and optionally D to give
branched
polyesters, it is of course also possible to use mixtures of different
components A, mixtures of
different components B, optionally mixtures of different components C and/or
optionally
mixtures of different components D. Preference is given to using mixtures with
up to three
different components A, mixtures with up to three different components B
and/or optionally
mixtures with up to three different components C. Particular preference is
given to using
mixtures with up to two different components A, mixtures with up to two
different components B
and/or optionally mixtures with up to two different components C. In
particular, in the reaction of
the components A, B, optionally C and optionally D to give branched
polyesters, preference is
given to using in each case one compound A, B and optionally C.
The carboxylic acids (C2) of component C carry no sulfonic acid or sulfonate
groups.
The branched polyesters with sulfonate groups of the invention are preferably
dendritic, in
particular hyperbranched, polyesters.
The term dendritic polymer or else highly branched polymer is the generic term
for a series of
different branched molecular structures. It covers, for example, dendrimers,
star polymers and
hyperbranched polymers.
Dendrimers are formed starting from a center (as a rule a small molecule with
a plurality of
reactive end groups), onto which, through a constantly repeating controlled
reaction sequence,
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generation upon generation of a branching monomer is attached. Thus, with each
reaction step,
the number of monomer end groups in the resulting dendrimer increases
exponentially. A
characteristic feature of the dendrimers is the number of reaction stages
(generations) carried
out in their construction. On account of the uniform structure (in the ideal
case all of the
branches comprise exactly the same number of monomer units), dendrimers are
essentially
monodisperse, i.e. they generally have a defined molar mass. Molecularly as
well as structurally
uniform highly branched polymers are referred to below as dendrimers for
consistency.
Within the context of this invention, "hyperbranched polymers" are highly
branched polymers
which, in contrast to the dendrimers specified above, are both molecularly and
also structurally
nonuniform. Hyperbranched polymers therefore have a nonuniform molar mass
distribution
(polydispersity). To produce hyperbranched polymers, a distinction is made
between various
synthesis strategies. An overview of possible synthesis methods can be found
in C. Gao,
D. Yan, Prog. Polym. Sci. 29 (2004), 183.
As regards the definition of dendritic and hyperbranched polymers, see also
P.J. Flory, J. Am.
Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chemistry - A European Journal,
2000, 6,
No. 14, 2499.
Dendritic polymers can be characterized via their "degree of branching". As
regards the
definition of the "degree of branching", reference is made to H. Frey et al.,
Acta Polym. 1997,
48, 30. The degree of branching DB here is defined as DB (%) = (T + Z)/(T + Z
+ L) x 100,
where
T is the average number of terminally bonded monomer units,
is the average number of monomer units forming branches,
is the average number of the linearly bonded monomer units.
Dendrimers have in general a degree of branching DB of at least 99%,
specifically 99.9 to
100%.
Hyperbranched polymers preferably have a degree of branching DB of from 10 to
95%,
preferably 25 to 90% and in particular 30 to 80%.
The branched polyesters used according to the invention preferably have a
degree of branching
(DB) per molecule of from 10 to 95%, preferably from 10 to 90%, particularly
preferably from 10
to 80%, and in particular 20 to 80%.
Within the context of this invention, hyperbranched polyesters with or without
sulfonate groups
are understood as meaning uncrosslinked polyesters with or without sulfonate
groups which are
PF 72097 CA 02836849 2013-11-20
both structurally and molecularly nonuniform. Within the context of this
specification,
uncrosslinked means that a degree of crosslinking of less than 15% by weight,
preferably of
less than 10% by weight, determined over the insoluble fraction of the
polymer, is present.
5 The insoluble fraction of the polymer was determined by extraction for
four hours in a Soxhlet
apparatus with a solvent in which the polymer is soluble, for example
tetrahydrofuran,
dimethylacetamide or hexafluoroisopropanol, preferably tetrahydrofuran. After
drying the
residue to constant weight, the remaining residue is weighed.
In a preferred embodiment, the branched polyesters with sulfonate groups
according to the
invention are obtained using component D, where preferably less than 20 mol%
of component
D, based on the total amount of components A, B, C and D, are used. Preference
is given here
to using less than 10 mol% of component D, and very particular preference is
given to using
less than 5 mol%. Preferably, component D is selected from fatty acids or
fatty alcohols.
Suitable fatty acids or fatty alcohols can comprise 8 to 30 carbon atoms,
preferably 12 to 25,
and particularly preferably 16 to 20, carbon atoms.
Examples of suitable fatty acids are octanoic acid, isononanoic acid, capric
acid, undecanoic
acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric
acid, stearic acid,
nonadecanoic acid, arachic acid, behenic acid, oleic acid, linoleic acid,
linolenic acid, benzoic
acid, a- or 8-naphthalenic acid.
In a preferred embodiment of the branched polyesters with sulfonate groups,
the fraction of the
tri- or higher-functional component B in step a. is at least 30 mol%, based on
the total amount of
the components A, B, C and D, particularly preferably at least 35 mol% and
very particularly
preferably at least 40 mol%.
In a further preferred embodiment of the branched polyesters with sulfonate
groups, in step a.,
at least 5 mol% of components A are used, based on the total amount of
components A, B, C
and D. Preference is given here to using at least 10 mol%. Preferably, the
fraction of component
A, based on the total amount of components A, B, C and D, is at most 60 mol%,
preferably at
most 50 mol% and very particularly preferably at most 40 mol%.
Within the context of the branched polyesters with sulfonate groups according
to the invention,
the amount of hydrogen sulfite in step b can vary within a wide range
depending on the
particular application. Further, preference is given to using 10 to 95 mol%,
particularly
preferably from 20 to 92 mol% and in particular from 30 to 90 mol%, of
hydrogen sulfite, based
on the amount of a,f3-olefinically unsaturated dicarboxylic acids (A2).
The molecular weight of the branched polyesters were determined prior to the
reaction with
hydrogen sulfite by means of gel permeation chromatography (GPC) compared with
polymethyl
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methacrylate (PMMA) as standard. For this, dimethylacetamide or
tetrahydrofuran were used as
eluents. The method is described in Analytiker Taschenbuch [Analytical
handbook] Vol. 4,
pages 433-442, Berlin 1984.
The thus determined weight-average molecular weights (M) of the polyesters A
before the
reaction with hydrogen sulfite are in the range from 500 g/mol to 50 000
g/mol, preferably in the
range from 750 g/mol to 25 000 g/mol and very particularly preferably in the
range from
1000 g/mol to 15 000 g/mol.
The branched polyesters prior to the reaction with hydrogen sulfite have acid
numbers of from
10 to 500 mg KOH/g polymer, preferably 15 to 400 mg KOH/g polymer and very
particularly
preferably 20 to 300 mg KOH/g polymer. The acid number was determined in
accordance with
DIN 53402.
The branched polyesters A prior to the reaction with hydrogen sulfite have
glass transition
temperatures in the range from -50 to +50 C, preferably -40 to +40 C and very
particularly
preferably -30 to +40 C. The glass transition temperature is determined by
means of DSC
(Differential Scanning Calorimetry).
Preferably, for the branched polyesters with sulfonate groups, the a,p-
olefinically unsaturated
dicarboxylic acids (A2) used are maleic acid, itaconic acid, fumaric acid,
citraconic acid,
mesaconic acid or glutaconic acid. Particular preference is given to maleic
acid and itaconic
acid, very particularly preferably maleic acid and derivatives thereof such as
maleic anhydride.
The dicarboxylic acids (A2) can either be used as such or in the form of
derivatives.
Derivatives of the dicarboxylic acids (A2) are preferably understood here as
meaning
- the relevant anhydrides in monomeric or polymeric form,
- mono- or dialkyl esters, preferably mono- or di-Ci-C4-alkyl esters,
particularly preferably
mono- or dimethyl esters or the corresponding mono- or diethyl esters,
also mono- and divinyl esters, and
- mixed esters, preferably mixed esters with different Ci-C4-alkyl
components, particularly
preferably mixed methyl ethyl esters.
Among these, the anhydrides and the mono- or dialkyl esters are preferred,
particular
preference being given to the anhydrides and the mono- or di-Ci-C4-alkyl
esters and very
particular preference being given to the anhydrides.
Within the context of this specification, Cl-C4-alkyl is methyl, ethyl,
isopropyl, n-propyl, n-butyl,
isobutyl, sec-butyl or tert-butyl, preferably methyl, ethyl and n-butyl,
particularly preferably
methyl and ethyl and very particularly preferably methyl.
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Within the context of the present invention, it is also possible to use a
mixture of a dicarboxylic
acid and one or more of its derivatives. Equally, within the context of the
present invention, it is
possible to use a mixture of two or more different derivatives of one or more
dicarboxylic acids.
Preferably, for the branched polyesters with sulfonate groups, the tri- or
higher-functional
alcohols (By where y is greater than or equal to 3) used are
glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane,
bis(trimethylolpropane),
trimethylolbutane, trimethylolpentane, 1,2,4-butanetriol, 1,2,6-hexanetriol,
tris(hydroxymethyl)-
amine, tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, pentaerythritol,
diglycerol, triglycerol
or higher condensation products of glycerol, di(trimethylolpropane),
di(pentaerythritol),
tris(hydroxymethyl)isocyanurate, tris(hydroxyethyl)isocyanurate (THEIC),
tris(hydroxypropyI)-
isocyanurate,
sugars or sugar alcohols such as, for example, glucose, fructose or sucrose,
sugar alcohols
such as e.g. sorbitol, mannitol, threitol, erythritol, adonitol (ribitol),
arabitol (lyxitol), xylitol,
dulcitol (galactitol), maltitol, isomalt, or inositol
tri- or higher-functional polyetherols based on tri- or higher-functional
alcohols, which are
obtained by reaction with ethylene oxide, propylene oxide and/or butylene
oxide, particularly
preferably with propylene oxide,
or tri- or higher-functional polyesterols based on tri- or higher-alcohols,
which are obtained by
reaction with caprolactone.
The tri- or higher-functional alcohols (By where y is greater than or equal to
3) particularly
preferably used here are
glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane,
di(trimethylolpropane),
pentaerythritol, sucrose or sorbitol, and also polyetherols thereof based on
ethylene oxide
and/or propylene oxide
and in particular
glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane,
pentaerythritol or
polyetherols thereof based on propylene oxide.
For the branched polyesters with sulfonate groups, the difunctional carboxylic
acids (C2) without
a,6-olefinically unsaturated bonds preferably used are
aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a,w-
dicarboxylic acid,
dodecane-a,w-dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic
acid, cis- and
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trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-
dicarboxylic acid, cis-
and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-1,3-
dicarboxylic acid,
aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid or
terephthalic acid.
The specified dicarboxylic acids can also be substituted with one or more
radicals, selected
from
Cl-C20-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl,
isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl,
trimethylpentyl, n-nonyl, n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl,
C2-C20-alkenyl groups, for example butenyl, hexenyl, octenyl, decenyl,
dodecenyl, tetradecenyl,
hexadecenyl, octadecenyl or eicosenyl,
C3-C12-cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and
cyclododecyl; preference
being given to cyclopentyl, cyclohexyl and cycloheptyl;
alkylene groups such as methylene or ethylidene or
C6-C14-aryl groups such as, for example, phenyl, 1-naphthyl, 2-naphthyl, 1-
anthryl, 2-anthryl,
9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-
phenanthryl,
preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.
Examples of representatives of substituted dicarboxylic acids or derivatives
thereof which may
be mentioned are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic
acid, 2-methyl-
succinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, 3,3-
dimethylglutaric acid, dodecenyl-
succinic acid, hexadecenylsuccinic acid, octadecenylsuccinic acid, and also
reaction products of
polyisobutylenes with an enophile selected from the group fumaryl dichloride,
fumaric acid,
maleoyl dichloride, maleic anhydride and/or maleic acid, preferably with
maleic anhydride or
maleoyl dichloride, particularly preferably with maleic anhydride, to give
succinic acid
derivatives substituted with polyisobutylene, in which the polyisobutylenyl
group can have a
number-average molecular weight Mn of from 100 to 100 000 daltons. This
reaction takes place
by the methods known to the person skilled in the art and preferably as
described in the
German laid-open specifications DE-A 195 19 042, therein preferably from p. 2,
I. 39 to p. 4,1. 2
and particularly preferably from p. 3, II. 35-58, and DE-A 43 19 671, therein
preferably from p. 2,
I. 30 to 1. 68, and DE-A 43 19 672, therein preferably from p. 2, I. 44 to p.
3, I. 19, described
methods for the reaction of polyisobutylenens with enophiles.
Furthermore, mixtures of two or more of the aforementioned dicarboxylic acids
can be used. For
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example, one to six, preferably one to four, particularly preferably one to
three, very particularly
preferably one to two and especially one, dicarboxylic acid can be used.
The dicarboxylic acids can be used either as such or in the form of
derivatives.
Derivatives are preferably understood as meaning
- the relevant anhydrides in monomeric or polymeric form,
- mono- or dialkyl esters, preferably mono- or di-Ci-C4-alkyl esters,
particularly preferably
mono- or dimethyl esters or the corresponding mono- or diethyl esters,
- also mono- and divinyl esters, and also
- mixed esters, preferably mixed esters with different Ci-C4-alkyl
components, particularly
preferably mixed methyl ethyl esters.
Among these, the anhydrides and the mono- or dialkyl esters are preferred,
particular
preference being given to the anhydrides and the mono- or di-Ci-C4-alkyl
esters and very
particularly preferably being given to the anhydrides.
For the branched polyesters with sulfonate groups as difunctional carboxylic
acids (C2) without
a,3-olefinically unsaturated bonds, particular preference is given to using
aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a,w-
dicarboxylic acid,
dodecane-a,w-dicarboxylic acid, dodecenylsuccinic acid, hexadecenylsuccinic
acid or octa-
decenylsuccinic acid.
For the branched polyesters with sulfonate groups as difunctional alcohols
(B2) without
a,8-olefinically unsaturated bonds, preference is given to using
ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-
1,3-diol, butane-1,4-
diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol,
pentane-1,5-diol,
pentane-2,3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-
1,4-diol, hexane-
1,5-diol, hexane-1,6-diol, hexane-2,5-diol, heptane-1,2-diol, 1,7-heptanediol,
1,8-octanediol,
1,2-octanediol, 1,9-nonanediol, 1,2-decanediol,
1,10-decanediol, 1,2-dodecanediol,
1,12-dodecanediol, 1,5-hexadiene-3,4-diol, 1,2- and 1,3-cyclopentanediols, 1,2-
, 1,3- and
1,4-cyclohexanediols, 1,1-, 1,2-, 1,3- and 1,4-bis(hydroxymethyl)cyclohexanes,
1,1-, 1,2-, 1,3-
and 1,4-bis(hydroxyethyl)cyclohexanes, neopentyl glycol, (2)-methyl-2,4-
pentanediol, 2,4-di-
methy1-2,4-pentanediol, 2-ethy1-1,3-hexanediol, 2,5-dimethy1-2,5-hexanediol,
2,2,4-trimethy1-1,3-
pentanediol, pinacol, diethylene glycol, triethylene glycol, isosorbide,
dipropylene glycol,
tripropylene glycol,
polyethylene glycols HO(CH2CH20)n-H, polypropylene glycols HO(CH[CH3]CH20),rH,
PF 72097 CA 02836849 2013-11-20
polybutylene glycols HO(CH[CH3]CH2CH20),-H, where n is an integer and n is a
4, preferably n
is an integer from the range from 4 to 40, particularly preferably from 4 to
20, polyethylene
polypropylene glycols, where the order of the ethylene oxide or propylene
oxide units can be
blockwise or random,
5
or polytetramethylene glycols, poly-1,3-propanediols or polycaprolactones with
a molecular
weight of up to 5000 g/mol, preferably with a molecular weight up to 2000
g/mol.
As difunctional alcohols (B2), particular preference is given here to using
polyethylene glycols HO(CH2CH20)n-H, polypropylene glycols HO(CH[CH3]CH20)n-H,
polybutylene glycols HO(CH[CH3]CH2CH20)n-H, where n is an integer and n is 4,
preferably n
is an integer from the range from 4 to 40, particularly preferably from 4 to
20,
or polytetramethylene glycols, poly-1,3-propanediols or polycaprolactones with
a molecular
weight of up to 5000 g/mol, preferably with a molecular weight up to 2000
g/mol.
In a preferred embodiment, the branched polyesters with sulfonate groups are
based on a
number of different components A, B, C and D, which is less than or equal to
4, i.e. in step a. 4
or fewer different components A, B, C and D are used. Preferably, the number
of different
components A, B, C and D is 3. The number of different components A, B, C and
D is of course
at least 2.
Preferably, for the branched polyesters with sulfonate groups, the amount of
component A is
greater than 20 mol%, preferably greater than 30 mol%, particularly preferably
greater than
50 mol%, based on the total amount of carboxylic acids of components A and C
together.
A further embodiment of the invention is given by mixtures of the branched
polyesters with
sulfonate groups according to the invention. Besides the branched polyesters
of the invention,
such mixtures comprise further constituents such as solvents or surfactants.
These mixtures are
preferably detergent and cleaner formulations.
The detergent and cleaner formulations in which the branched polyesters with
sulfonate groups
according to the invention can be used are in powder form, granule form,
tablet form, paste
form, gel form or liquid. Examples thereof are heavy-duty detergents, mild-
action detergents,
color detergents, wool detergents, net curtain detergents, modular detergents,
washing tablets,
bar soaps, stain salts, laundry starches and stiffeners, ironing aids. They
comprise at least 0.1%
by weight, preferably between 0.1 and 10% by weight and particularly
preferably 0.2 to 3% by
weight, of the branched polyesters with sulfonate groups according to the
invention. The
formulations are to be adapted according to their intended use in terms of
their composition to
the type of textiles to be washed or the surfaces to be cleaned. They comprise
conventional
detergent and cleaner ingredients, as correspond to the prior art.
Representative examples of
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such detergent and cleaner ingredients are described below.
The total concentration of surfactants in the finished detergent and cleaner
formulation can be
from 0.1 to 99% by weight, preferably from 5 to 80% by weight, particularly
preferably from 10 to
50% by weight. The surfactants used may be anionic, nonionic, amphoteric or
cationic. It is also
possible to use mixtures of the specified surfactants. Preferred detergent and
cleaner
formulations comprise anionic and/or nonionic surfactants and mixtures thereof
with further
surfactants.
Corresponding surfactants are known from the prior art and are described, for
example, in
EP 1 035 194 A2 (sections [0021] to [0047]).
These mixtures are preferably textile auxiliaries, detergents and cleaners for
textiles, additives
for detergents and cleaners of textiles, washing auxiliaries, laundry after-
treatment compositions
or cleaners, rinses or detergents for hard surfaces. The branched polyesters
of the invention
can be incorporated directly into the formulations (mixtures) in their various
presentation forms
by methods known to the person skilled in the art. In this connection, mention
is to be made of
solid formulations such as powders, granules, tablets, pastes, gels and liquid
formulations.
The invention therefore further provides the use of the branched polyesters
with sulfonate
groups according to the invention, or mixtures thereof as soil release
polymers, preferably as
textile auxiliaries, detergents and cleaners for textiles, additives for
detergents and cleaners of
textiles, washing auxiliaries, laundry after-treatment compositions or
cleaners, rinses or
detergents for hard surfaces. The branched polyesters with sulfonate groups
are used here as
so-called "soil release" polymers or "soil repellants", and impart soil-
repelling properties to the
treated surfaces. In particular, the branched polyesters with sulfonate groups
according to the
invention lead to the increase in the cleaning power of detergents and
cleaners toward oily and
greasy soilings.
The invention further provides the use of the branched polyesters with
sulfonate groups
according to the invention, or mixtures thereof, as graying inhibitors,
preferably for textile fabrics
(textiles). The branched polyesters with sulfonate groups are used here as so-
called "anti
graying" polymers, and ensure that the dirt detached from the fiber remains
suspended in the
wash liquor and does not become attached again to the textile fabric. In
particular, the branched
polyesters with sulfonate groups according to the invention lead to a graying
inhibition in the
case of textile fabrics comprising polyester. In particular, the branched
polyesters with sulfonate
groups according to the invention are suitable as graying inhibitors for
liquid detergents.
The invention further provides the use of the branched polyesters with
sulfonate groups
according to the invention in aqueous solutions or preparations for achieving
a soil release
finish on textiles.
PF 72097 CA 02836849 2013-11-20
12
A preferred embodiment of the mixtures according to the invention is given by
a cleaning
formulation comprising, as components:
a) from 0.1 to 20% by weight of at least one polymer according to the
invention
b) from 5 to 80% by weight of surfactants
c) from 0.1 to 50% by weight of builders
d) from 0-30% by weight of bleaching system
e) 0-20% by weight of nonaqueous solvents
f) further auxiliaries, such as alkali carriers, antifoams, enzymes (e.g.
lipases, proteases,
amylases, cellulases), antifoams, dyes, fragrances, further additional graying
inhibitors,
color transfer inhibitors, thickeners, solubility promoters and water.
The sum of the components from a) to f) gives 100% by weight.
The quantitative ratios of the individual components are adjusted by the
person skilled in the art
depending on the particular field of use of the cleaning formulation.
The nonionic surfactants used are preferably alkoxylated, advantageously
ethoxylated, in
particular primary alcohols having preferably 8 to 18 carbon atoms and, on
average, 1 to 12 mol
of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can
be linear or
preferably 2-methyl-branched and/or can comprise linear and methyl-branched
radicals in a
mixture, as are customarily present in oxo alcohol radicals. In particular,
however, preference is
given to alcohol ethoxylates with linear or branched radicals from alcohols of
native or
petrochemical origin having 12 to 18 carbon atoms, for example from coconut
alcohol, palm
alcohol, tallow fat alcohol or oleyl alcohol, and, on average, 2 to 8 EO per
mole of alcohol. The
preferred ethoxylated alcohols include, for example, C12-C14-alcohols with 3
EO, 5 EO, 7 EO or
9 EO, C9-C11-alcohol with 7 EO, C13-C15-alcohols with 3 EO, 5 EO, 7 EO or 9
EO, C12-C18-
alcohols with 3 EO, 5 EO, 7 EO or 9 EO and mixtures of these, such as mixtures
of C12-C14-
alcohol with 3 EO and C12-C15-alkohol with 7 EO, 2 propylheptanol with 3 to 9
EO. Mixtures of
short-chain alcohol ethoxylates (e.g. 2-propylheptanol x 7 EO) and long-chain
alcohol
ethoxylates (e.g. C16,18 x 7 EO). The stated degrees of ethoxylation are
statistical average
values (number-average, Mn) which can be an integer or a fraction for a
specific product.
Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow
range ethoxylates,
NRE). In addition to these nonionic surfactants, fatty alcohols with more than
12 EO can also be
used. Examples thereof are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40
EO. Nonionic
surfactants which comprise EO and PO groups together in the molecule can also
be used. In
this connection, it is possible to use block copolymers with EO-PO block units
or PO-E0 block
units, or else EO-PO-E0 copolymers or PO-E0-P0 copolymers. It is of course
also possible to
use mixed alkoxylated nonionic surfactants in which EO and PO units are not
distributed
blockwise, but randomly. Such products are obtainable by the simultaneous
action of ethylene
oxide and propylene oxide on fatty alcohols.
PF 72097 CA 02836849 2013-11-20
13
Moreover, as further nonionic surfactants, it is also possible to use alkyl
glycosides of the
general formula (1)
R10(G)), (1)
in which R1 is a primary straight-chain or methyl-branched, in particular 2-
methyl-branched
aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is a
glycoside unit
having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization
x, which
indicates the distribution of monoglycosides and oligoglycosides, is any
desired number
between 1 and 10; preferably, xis 1.2 to 1.4.
A further class of preferably used nonionic surfactants, which are used either
as the sole
nonionic surfactant or in combination with other nonionic surfactants, are
alkoxylated, preferably
ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters,
preferably having 1 to 4
carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as
are described, for
example, in the Japanese patent application JP 58/217598 or which are
preferably prepared by
the process described in the international patent application WO-A-90/13533.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-
dimethylamine oxide
and N-tallow-alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid
alkanolamides may also
be suitable. The amount (weight) of these nonionic surfactants is preferably
not more than that
of the ethoxylated fatty alcohols, in particular not more than half of it.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula
(2),
0
2 [Z] (2)
I 3
in which R2C(=0) is an aliphatic acyl radical having 6 to 22 carbon atoms, R3
is hydrogen, an
alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear
or branched
polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl
groups. The
polyhydroxy fatty acid amides are known substances which can usually be
obtained by
reductive amination of a reducing sugar with ammonia, an alkylamine or an
alkanolamine and
subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty
acid chloride.
The group of polyhydroxy fatty acid amides also includes compounds of the
formula (3)
PF 72097 CA 02836849 2013-11-20
14
R¨O¨R6 (3)
4
RN
[Z]
0
in which R4 is a linear or branched alkyl or alkenyl radical having 7 to 12
carbon atoms, R5 is a
linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an
arylene radical
5 having 6 to 8 carbon atoms and R6 is a linear, branched or cyclic alkyl
radical or an aryl radical
or an oxy-alkyl radical having 1 to 8 carbon atoms, where C1-C4-alkyl or
phenyl radicals are
preferred, and [41 is a linear polyhydroxyalkyl radical whose alkyl chain is
substituted with at
least two hydroxyl groups, or alkoxylated, preferably ethoxylated or
propoxylated, derivatives of
this radical. [41 is preferably obtained by reductive amination of a sugar,
for example glucose,
fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-
aryloxy-
substituted compounds can then be converted to the desired polyhydroxy fatty
acid amides for
example as in WO-A-95/07331 by reaction with fatty acid methyl esters in the
presence of an
alkoxide as catalyst.
The content of non-ionic surfactants in the liquid detergents or cleaners is
preferably from 5 to
40% by weight, preferably from 7 to 30% by weight and in particular from 9 to
25% by weight, in
each case based on the total composition.
The anionic surfactants used are, for example, those of the sulfonate and
sulfate type. Suitable
surfactants of the sulfonate type are preferably C9-C13-
alkylbenzenesulfonates, olefinsulfonates,
i.e. mixtures of alkene- and hydroxyalkanesulfonates, and also disulfonates,
as are obtained, for
example, from C12-C18-monoolefins with terminal or internal double bond by
sulfonation with
gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the
sulfonation products.
Also suitable are alkanesulfonates which are obtained from C12-C18-alkanes,
for example by
sulfochlorination or sulfoxidation with subsequent hydrolysis or
neutralization. Likewise, the
esters of a-sulfo fatty acids (ester sulfonates), for example the a-sulfonated
methyl esters of the
hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters.
Fatty acid glycerol
esters are to be understood as meaning the mono-, di- and triesters, and
mixtures thereof, as
are obtained in the preparation by esterification of a monoglycerol with 1 to
3 mol of fatty acid or
during the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
Preferred sulfated fatty
acid glycerol esters here are the sulfation products of saturated fatty acids
having 6 to
22 carbon atoms, for example of caproic acid, caprylic acid, capric acid,
myristic acid, lauric
acid, palmitic acid, stearic acid or behenic acid.
The alk(en)yl sulfates are preferably the alkali metal and in particular the
sodium salts of the
sulfuric acid half-esters of C12-C18-fatty alcohols, for example of coconut
fatty alcohol, tallow
fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl
alcohol or of the Clo-C20-oxo
PF 72097 CA 02836849 2013-11-20
alcohols and those half-esters of secondary alcohols of these chain lengths.
Furthermore,
preference is given to alk(en)yl sulfates of the specified chain length which
comprise a
synthetic, petrochemical-based straight-chain alkyl radical which have an
analogous
degradation behavior to the equivalent compounds based on fatty chemical raw
materials. From
5 a washing point of view, the C12-C16-alkyl sulfates and C12-C15-alkyl
sulfates and also C14-C15-
alkyl sulfates are preferred. 2,3-Alkyl sulfates, which are prepared, for
example, in accordance
with the US patent specifications 3,234,258 or 5,075,041 and can be obtained
as commercial
products from the Shell Oil Company under the name DAN , are also suitable
anionic
surfactants.
The sulfuric acid monoesters of the straight-chain or branched C7-C21-alcohols
ethoxylated with
1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cs-Cu-alcohols with on
average
3.5 mol of ethylene oxide (EO) or C12-Ci8-fatty alcohols with 1 to 4 EO, are
also suitable. On
account of their high foaming behavior, they are used in cleaners only in
relatively small
amounts, for example in amounts from 1 to 5% by weight.
Further suitable anionic surfactants are also the salts of alkylsulfosuccinic
acid, which are also
referred to as sulfosuccinates or as sulfosuccinic acid esters and which
constitute monoesters
and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols
and in particular
ethoxylated fatty alcohols. Preferred sulfosuccinates comprise Cs-Cis-fatty
alcohol radicals or
mixtures thereof. Particularly preferred sulfosuccinates comprise a fatty
alcohol radical derived
from ethoxylated fatty alcohols. In this connection, particular preference is
in turn given to
sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated
fatty alcohols with a
narrow homolog distribution. It is likewise also possible to use
alk(en)ylsuccinic acid having
preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
Particularly preferred anionic surfactants are soaps. Saturated and
unsaturated fatty acid soaps,
such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid,
(hydrogenated) erucic
acid and behenic acid, and also soap mixtures derived in particular from
natural fatty acids, for
example coconut, palm kernel, olive oil or tallow fatty acids, are suitable.
The anionic surfactants including the soaps can be present in the form of
their sodium,
potassium or ammonium salts, and also as soluble salts of organic bases, such
as mono-, di- or
triethanolamine. Preferably, the anionic surfactants are present in the form
of their sodium or
potassium salts, in particular in the form of the sodium salts.
The content of anionic surfactants in preferred liquid detergents or cleaners
is 2 to 50% by
weight, preferably 4 to 40% by weight and in particular 5 to 35% by weight, in
each case based
on the total composition. It is particularly preferred that the amount of
fatty acid soap is at least
2% by weight and particularly preferably at least 4% by weight and
particularly preferably at
least 6% by weight.
PF 72097 CA 02836849 2013-11-20
16
In addition to the polymer according to the invention and to the
surfactant(s), the liquid
detergents or cleaners can comprise further ingredients which further improve
the application
and/or esthetic properties of the liquid detergent or cleaner. As a rule, in
addition to the polymer
according to the invention and to surfactant(s), preferred compositions
comprise one or more
substances from the group of thickeners, builders, bleachers, bleach
activators, enzymes,
electrolytes, nonaqueous solvents, pH extenders, fragrances, perfume carriers,
fluorescent
agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition
agents, optical
brighteners, further additional graying inhibitors, antishrink agents,
anticrease agents, color
transfer inhibitors, antimicrobial active ingredients, germicides, fungicides,
antioxidants,
corrosion inhibitors, antistatics, ironing aids, phobicization and
impregnation agents, swelling
and nonslip agents, and also UV absorbers.
Thickeners which can be used are so-called associative thickeners. Examples of
thickeners are
described in WO 2009/019225 A2, EP-A 0 013 836 or WO 2006/016035.
Builders which may be present in the liquid detergents or cleaners are, in
particular, silicates,
aluminum silicates (in particular zeolites), carbonates, salts of organic di-
and polycarboxylic
acids, and mixtures of these substances.
Suitable low molecular weight polycarboxylates as organic builders are, for
example:
C4-C20-di-, -tri- and -tetracarboxylic acids, such as, for example, succinic
acid, propanetri-
carboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid
and alkyl- and
alkylenesuccinic acids with C2-C16-alkyl or -alkylene radicals;
C4-C20-hydyroxycarboxylic acids, such as, for example, malic acid, tartaric
acid, gluconic acid,
glutaric acid, citric acid, lactobionic acid and sucrose mono-, -di- and -
tricarboxylic acid;
aminopolycarboxylates, such as, for example, nitrilotriacetic acid,
methylglycinediacetic acid,
alaninediacetic acid, ethylenediaminetetraacetic acid and serinediacetic acid,
N,N-bis-
(carboxylatomethyl)-L-glutamate (GLDA);
salts of phosphonic acids, such as, for example, hydroxyethanediphosphonic
acid, ethylene-
diamine tetra(methylenephosphonate) and diethylenetriamine
penta(methylenephosphate).
Suitable oligomeric or polymeric polycarboxylates as organic builders are, for
example:
oligomaleic acids, as are described, for example, in EP-A 0 451 508 and EP-A 0
396 303;
co- and terpolymers of unsaturated C4-C8-dicarboxylic acids, where
monoethylenically
unsaturated monomers
PF 72097 CA 02836849 2013-11-20
17
from group (i) in amounts of up to 95% by weight
from group (ii) in amounts of up to 60% by weight
from group (iii) in amounts of up to 20% by weight
may be present in copolymerized form as comonomers.
Suitable unsaturated C4-C8-dicarboxylic acids here are, for example, maleic
acid, fumaric acid,
itaconic acid and citraconic acid (methylmaleic acid). Preference is given to
maleic acid.
Group (i) comprises monoethylenically unsaturated C3-C8-monocarboxylic acids,
such as, for
example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.
From group (i),
preference is given to using acrylic acid and methacrylic acid.
Group (ii) comprises monoethylenically unsaturated C2-C22-olefins, vinyl alkyl
ethers with Ci-C8-
alkyl groups, styrene, vinyl esters of Ci-C8-carboxylic acid, (meth)acrylamide
and vinyl-
pyrrolidone. From group (ii), preference is given to using C2-C6-olefins,
vinyl alkyl ethers with
Cl-C4-alkyl groups, vinyl acetate and vinyl propionate.
Group (iii) comprises (meth)acrylic esters of Cl-C8-alcohols,
(meth)acrylonitrile,
(meth)acrylamides, (meth)acrylamides of C1-C8-amines, N-vinylformamide and
vinylimidazole.
If the polymers of group (ii) comprise vinyl esters in copolymerized form,
these may also be
present in partially or completely hydrolyzed form to give vinyl alcohol
structural units. Suitable
co- and terpolymers are known, for example, from US 3,887,806 and SE-A 43 13
909.
Copolymers of dicarboxylic acids suitable as organic builders are preferably:
copolymers of maleic acid and acrylic acid in the weight ratio 10:90 to 95:5,
particularly
preferably those in the weight ratio 30:70 to 90:10 with molar masses of from
10 000 to
150000;
terpolymers of maleic acid, acrylic acid and a vinyl ester of a Cl-C3-
carboxylic acid in the weight
ratio 10(maleic acid):90(acrylic acid + vinyl ester) to 95(maleic
acid):10(acrylic acid + vinyl
ester), where the weight ratio of acrylic acid to vinyl ester can vary in the
range from 20:80 to
80:20, and particularly preferably
terpolymers of maleic acid, acrylic acid and vinyl acetate or vinylpropionate
in the weight ratio
20(maleic acid):80(acrylic acid + vinyl ester) to 90(maleic acid):10(acrylic
acid + vinyl ester),
where the weight ratio of acrylic acid to the vinyl ester can vary in the
range from 30:70 to
70:30;
copolymers of maleic acid with C2-C8-olefins in the molar ratio 40:60 to
80:20, where
,
PF 72097 CA 02836849 2013-11-20
18
copolymers of maleic acid with ethylene, propylene or isobutane in the molar
ratio 50:50 are
particularly preferred.
Graft polymers of unsaturated carboxylic acids on low molecular weight
carbohydrates or
hydrogenated carbohydrates, cf. US 5,227,446, DE-A 44 15 623, DE-A 43 13 909,
are likewise
suitable as organic builders.
Suitable unsaturated carboxylic acids here are, for example, maleic acid,
fumaric acid, itaconic
acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and
vinylacetic acid, and also
mixtures of acrylic acid and maleic acid which are grafted on in amounts of
from 40 to 95% by
weight, based on the component to be grafted.
For the modification, additionally up to 30% by weight, based on the component
to be grafted, of
further monoethylenically unsaturated monomers may be present in copolymerized
form.
Suitable modifying monomers are the abovementioned monomers in groups (ii) and
(iii).
Suitable graft bases are degraded polysaccharides, such as, for example,
acidically or
enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated
or reductively
aminated) degraded polysaccharides, such as, for example, mannitol, sorbitol,
aminosorbitol
and glucamine, and also polyalkylene glycols with molar masses up to Mw = 5000
g/mol (weight
average), such as, for example, polyethylene glycols, ethylene oxide/propylene
oxide or
ethylene oxide/butylene oxide block copolymers, random ethylene
oxide/propylene oxide or
ethylene oxide/butylene oxide copolymers, alkoxylated mono- or polybasic Cl-
C22-alcohols, cf.
US 4,746,456.
From this group, preference is given to using grafted degraded or degraded
reduced starches
and grafted polyethylene oxides, where 20 to 80% by weight of monomers, based
on the graft
component, are used in the graft polymerization. For the grafting, preference
is given to using a
mixture of maleic acid and acrylic acid in the weight ratio of from 90:10 to
10:90.
Polyglyoxylic acids as organic builders are described, for example, in EP-B 0
001 004,
US 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the
polyglyoxylic acids
can have different structures.
Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic
builders are
known, for example, from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and
EP-A 0 581 452.
Preferably, the organic builders used are also polyaspartic acid or
cocondensates of aspartic
acid with further amino acids, C4-C25-mono- or -dicarboxylic acids and/or C4-
C25-mono- or
-diamines. Particular preference is given to using polyaspartic acids modified
with C6-C22-mono-
or -dicarboxylic acids or with C6-C22-mono- or -diamines and prepared in
phosphorus-containing
PF 72097 CA 02836849 2013-11-20
19
acids.
Condensation products of citric acid with hydroxycarboxylic acids or
polyhydroxy compounds as
organic builders are known, for example, from WO-A 93/22362 and WO-A 92/16493.
Carboxyl-
group-comprising condensates of this type usually have molar masses M, up to
10 000,
preferably up to 5000.
Among the compounds which produce H202 in water and can serve as bleaches,
sodium
perborate tetrahydrate and sodium perborate monohydrate have particular
importance. Further
bleaches that can be used are, for example, sodium percarbonate,
peroxypyrophosphates,
citrate perhydrates, and peracidic salts or peracids that produce H202, such
as perbenzoates,
peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic
acid.
In order to achieve an improved bleaching effect during washing at
temperatures of 60 C and
below, bleach activators can be incorporated into the detergents or cleaners.
Bleach activators
which can be used are compounds which, under perhydrolysis conditions, produce
aliphatic
peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2
to 4 carbon
atoms, and/or optionally substituted perbenzoic acid. Substances which carry 0-
and/or N-acyl
groups of the specified number of carbon atoms and/or optionally substituted
benzoyl groups
are suitable. Preference is given to polyacylated alkylenediamines, in
particular tetraacetyl-
ethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-
diacety1-2,4-dioxo-
hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular
tetraacetylglycoluril
(TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated
phenolsulfonates,
in particular n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS),
carboxylic acid
anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in
particular triacetin,
ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
In addition to the conventional bleach activators, or instead of them, it is
also possible to
incorporate so-called bleach catalysts into the liquid detergents or cleaners.
These substances
are bleach-boosting transition metal salts or transition metal complexes, such
as, for example,
Mn-, Fe-, Co-, Ru- or Mo-salene complexes or -carbonyl complexes. It is also
possible to use
Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod
ligands, and also
Co-, Fe-, Cu- and Ru-amine complexes as bleach catalysts.
Suitable enzymes are in particular those from the classes of the hydrolases,
such as the
proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases and
other glycosyl
hydrolases and mixtures of said enzymes. All of these hydrolases contribute
during washing to
the removal of stains such as protein-, fat- or starch-containing stains and
graying. Cellulases
and other glycosyl hydrolases can moreover contribute to the color retention
and to increasing
the softness of the textile by removing pilling and microfibrils.
Oxyreductases can also be used
for the bleaching or for the inhibition of color transfer. Enzymatic active
ingredients obtained
from bacterial strains or fungi such as Bacillus subtilis, Bacillus
licheniformis, Streptomyceus
PF 72097 CA 02836849 2013-11-20
griseus and Humicola insolens are particularly well suited. Preference is
given to using
proteases of the subtilisin type and in particular proteases which are
obtained from Bacillus
lentus. Here, enzyme mixtures, for example of protease and amylase or protease
and lipase or
lipolytic enzymes or protease and cellulase or of cellulase and lipase or
lipolytic enzymes or of
5 protease, amylase and lipase or lipolytic enzymes or protease, lipase or
lipolytic enzymes and
cellulase, but in particular protease and/or lipase-containing mixtures or
mixtures with lipolytic
enzymes are of particular interest. Examples of such lipolytic enzymes are the
known cutinases.
Peroxidases or oxidases have also proven suitable in some cases. Suitable
amylases include,
in particular, a-amylases, isoamylases, pullulanases and pectinases. The
cellulases used are
10 preferably cellobiohydrolases, endoglucanases and (3-glucosidases, which
are also called
cellobiases, or mixtures of these. Since different types of cellulase differ
in their CMCase and
avicelase activities, the desired activities can be established through
targeted mixtures of the
cellulases.
15 The enzymes can be adsorbed on carriers in order to protect them against
premature
decomposition. The fraction of the enzymes, enzyme mixtures or enzyme granules
can be, for
example, about 0.1 to 5% by weight, preferably 0.12 to about 2.5% by weight,
based on the
total formulation.
20 A broad number of highly diverse salts can be used as electrolytes from
the group of inorganic
salts. Preferred cations are the alkali and alkaline earth metals, preferred
anions are the halides
and sulfates. From the point of view of production, the use of NaCI or MgC12
in the compositions
is preferred. The fraction of electrolytes in the compositions is usually 0.5
to 5% by weight.
Nonaqueous solvents which can be used in the liquid detergents or cleaners
originate, for
example, from the group of mono- or polyhydric alcohols, alkanolamines or
glycol ethers,
provided they are miscible with water in the stated concentration range.
Preferably, the solvents
are selected from ethanol, n- or isopropanol, butanols, glycol, propane- or
butanediol, glycerol,
diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl
ether, ethylene glycol
ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether,
diethylene glycol
methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or
propyl ether,
dipropylene glycol monomethyl or -ethyl ether, diisopropylene glycol
monomethyl or -ethyl ether,
methoxy-, ethoxy- or butoxytriglycol, isobutoxyethoxy-2-propanol, 3-methyl-3-
methoxybutanol,
propylene glycol t-butyl ether, and mixtures of these solvents. Nonaqueous
solvents can be
used in the liquid detergents or cleaners in amounts between 0.5 and 20% by
weight, but
preferably below 12% by weight and in particular below 9% by weight, based on
the total
formulation.
In order to bring the pH of the liquid detergents or cleaners into the desired
range, the use of pH
extenders may be appropriate. All known acids or alkalis can be used here,
provided their use is
not precluded for applications-related or ecological reasons or for reasons of
consumer
protection. Usually, the amount of these extenders does not exceed 7% by
weight of the total
PF 72097 CA 02836849 2013-11-20
21
formulation.
In order to improve the esthetic impression of the liquid detergents or
cleaners, they can be
colored with suitable dyes. Preferred dyes, the selection of which presents no
difficulties at all to
the person skilled in the art, have a high storage stability and insensitivity
toward the other
ingredients of the compositions and to light, and also no marked substantivity
toward textile
fibers, in order not to stain these.
Suitable foam inhibitors which can be used in the liquid detergents or
cleaners are, for example,
soaps, paraffins or silicone oils, which can optionally be applied to carrier
materials.
Optical brighteners (so-called whiteners) can be added to the liquid
detergents or cleaners in
order to eliminate graying and yellowing of the treated textile fabrics. These
substances attach
to the fibers and bring about a brightening and quasi bleaching effect by
converting invisible
ultraviolet radiation into visible longer-wave light, where the ultraviolet
light absorbed from the
sunlight is emitted as pale bluish fluorescence and produces pure white with
the yellow shade of
grayed and/or yellowed laundry. Suitable compounds originate, for example,
from the substance
classes of the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids),
4,4'-distyrylbiphenylene,
methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines,
naphthalimides,
benzoxazole, benzisoxazole and benzimidazole systems, and the pyrene
derivatives substituted
by heterocycles. The optical brighteners are usually used in amounts between
0.03 and 0.3%
by weight, based on the finished composition.
Further additional graying inhibitors have the task of keeping the dirt
detached from the fibers
suspended in the liquor and thus preventing reattachment of the dirt. Of
suitability for this
purpose are water-soluble colloids mostly of an organic nature, for example
glue, gelatin, salts
of ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric
acid esters of cellulose
or of starch. Water-soluble polyamides comprising acidic groups are also
suitable for this
purpose. Furthermore, soluble starch preparations and starch products other
than those
mentioned above can be used, for example degraded starch, aldehyde starches,
etc. It is also
possible to use polyvinylpyrrolidone. However, preference is given to using
cellulose ethers,
such as carboxymethylcellulose (Na salt), methylcellulose,
hydroxyalkylcellulose and mixed
ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose,
methylcarboxy-
methylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight,
based on the
compositions.
Since textile fabrics, in particular made of rayon, viscose rayon, cotton and
mixtures thereof can
have a tendency to crease because the individual fibers are sensitive to
bending, folding,
pressing and squeezing at right angles to the fiber direction, the
compositions can comprise
synthetic anticrease agents. These include, for example, synthetic products
based on fatty
acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty
alkylolamides or fatty
alcohols, which are mostly reacted with ethylene oxide, or products based on
lecithin or
PF 72097 CA 02836849 2013-11-20
22
modified phosphoric acid esters.
To control microorganisms, the liquid detergents or cleaners can comprise
antimicrobial active
ingredients. A distinction is made here, depending on the antimicrobial
spectrum and action
mechanism, between bacteriostats and bactericides, fungistats and fungicides
etc. Important
substances from these groups are, for example, benzalkonium chlorides,
alkylarylsulfonates,
halophenols and phenol mercuriacetate.
In order to prevent undesired changes in the liquid detergents or cleaners
and/or the treated
textile fabrics caused by the effect of oxygen and other oxidative processes,
the compositions
can comprise antioxidants. This class of compound includes, for example,
substituted phenols,
hydroquinones, pyrocatechins and aromatic amines, and also organic sulfides,
polysulfides,
dithiocarbamates, phosphites and phosphonates.
Increased wear comfort can result from the additional use of antistats which
are additionally
added to the compositions. Antistats increase the surface conductivity and
thus permit an
improved discharging of charges formed. External antistats are generally
substances with at
least one hydrophilic molecule ligand and produce a more or less hygroscopic
film on the
surfaces. These mostly interface-active antistats can be divided into nitrogen-
containing
antistats (amines, amides, quaternary ammonium compounds), phosphorus-
containing antistats
(phosphoric acid esters) and sulfur-containing antistats (alkylsulfonates,
alkyl sulfates). External
antistats are described, for example, in the patent applications FR 1,156,513,
GB 873 214 and
GB 839 407. The lauryl (or stearyl)dimethylbenzylammonium chlorides disclosed
here are
suitable as antistats for textile fabrics and as additive for detergents where
a hand-modifying
effect is additionally achieved.
To improve the water absorption capacity, the rewettability of the treated
textile fabrics and to
facilitate ironing of the treated textile fabrics, silicone derivatives, for
example, can be used in
the liquid detergents or cleaners. These additionally improve the wash-out
behavior of the
compositions through their foam-inhibiting properties. Preferred silicone
derivatives are, for
example, polydialkyl- or alkylarylsiloxanes in which the alkyl groups have 1
to 5 carbon atoms
and are partially or completely fluorinated. Preferred silicones are
polydimethylsiloxanes which
can, optionally, be derivatized and then are aminofunctional or quaternized or
have Si-OH, Si-H
and/or Si-CI bonds. The viscosities of the preferred silicones at 25 C are in
the range between
100 and 100 000 mPas, it being possible to use the silicones in amounts
between 0.2 and 5%
by weight, based on the total composition.
Finally, the liquid detergents or cleaners can also comprise UV absorbers
which attach to the
treated textile fabrics and improve the photostability of the fibers.
Compounds which have these
desired properties are, for example, the compounds and derivatives of
benzophenone with
substituents in the 2 and/or 4 position that are effective as a result of
nonradiative deactivation.
Furthermore, substituted benzotriazoles, acrylates phenyl-substituted in the 3
position (cinnamic
PF 72097 CA 02836849 2013-11-20
23
acid derivatives), optionally with cyano groups in the 2 position,
salicylates, organic Ni
complexes, and natural substances such as umbelliferone and the endogenous
urocanic acid
are also suitable.
In order to avoid the decomposition of certain detergent ingredients catalyzed
by heavy metals,
it is possible to use substances which complex heavy metals. Suitable heavy
metal complexing
agents are, for example, the alkali metal salts of ethylenediaminetetraacetic
acid (EDTA), of
nitrilotriacetic acid (NTA) or methylglycinediacetic acid (MGDA), and also
alkali metal salts of
anionic polyelectrolytes such as polymaleates and polysulfonates.
A preferred class of complexing agents is the phosphonates, which are present
in preferred
liquid detergents or cleaners in amounts of from 0.01 to 2.5% by weight,
preferably 0.02 to 2%
by weight and in particular from 0.03 to 1.5% by weight. These preferred
compounds include, in
particular, organophosphonates, such as, for example, 1-hydroxyethane-1, 1-
diphosphonic acid
(HEDP), aminotri(methylenephosphonic acid) (ATMP),
diethylenetriaminepenta(methylene-
phosphonic acid) (DTPMP or DETPMP), and also 2-phosphonobutane-1,2,4-
tricarboxylic acid
(PBS-AM), which are mostly used in the form of their ammonium or alkali metal
salts.
The resulting aqueous liquid detergents or cleaners have no sediment; in a
preferred
embodiment, they are transparent or at least translucent. Preferably, the
aqueous liquid
detergents or cleaners have a visible light transmission of at least 30%,
preferably 50%,
particularly preferably 75%, most preferably 90%. Alternatively, the polymers
according to the
invention can be incorporated into opaque detergents or cleaners.
Besides these constituents, an aqueous detergent or cleaner can comprise
dispersed particles,
the diameter of which along their largest spatial expansion is 0.01 to 10 000
pm.
Particles may be microcapsules as well as granules, compounds and scented
beads, with
microcapsules being preferred.
The term "microcapsules" is understood as meaning aggregates which comprise at
least one
solid or liquid core which is surrounded by at least one continuous sheath, in
particular a sheath
made of polymer(s). Usually, these are finely dispersed liquid or solid phases
surrounded by
film-forming polymers, during the production of which the polymers, following
emulsification and
coacervation or interfacial polymerization, precipitate on to the material to
be enveloped. The
microscopically small capsules can be dried like powders. Besides single-core
microcapsules,
multicore aggregates are also known, also called microspheres, which comprise
two or more
cores distributed in the continuous coating material. Single-core or multicore
microcapsules can
additionally be surrounded by an additional second, third etc. sheath.
Preference is given to
single-core microcapsules with a continuous sheath. The sheath can consist of
natural,
semisynthetic or synthetic materials. Natural sheath materials are, for
example, gum arabic,
agar agar, agarose, maltodextrins, alginic acid and its salts, e.g. sodium
alginate or calcium
PF 72097 CA 02836849 2013-11-20
24
alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins,
gelatin, albumin,
shellac, polysaccharides, such as starch or dextran, sucrose and waxes.
Semisynthetic coating
materials are, inter alia, chemically modified celluloses, in particular
cellulose esters and ethers,
e.g. cellulose acetate, ethylcellulose, hydroxypropylcellulose,
hydroxypropylmethylcellulose and
carboxymethylcellulose, and also starch derivatives, in particular starch
ethers and esters.
Synthetic coating materials are, for example, polymers, such as polyacrylates,
polyamides,
polyvinyl alcohol or polyvinylpyrrolidone. In the interior of the
microcapsules, sensitive,
chemically or physically incompatible as well as volatile components (= active
ingredients) of the
aqueous liquid detergent or cleaner can be enclosed in a storage-stable and
transport-stable
manner. For example, optical brighteners, surfactants, complexing agents,
bleaches, bleach
activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme
stabilizers,
antimicrobial active ingredients, graying inhibitors, antiredeposition agents,
pH extenders,
electrolytes, foam inhibitors and UV absorbers may be present in the
microcapsules.
The microcapsules can also comprise cationic surfactants, vitamins, proteins,
preservatives,
detergency boosters or pearlizing agents. The fillings of the microcapsules
can be solids or
liquids in the form of solutions or emulsions or suspensions.
The microcapsules can have any desired form within the scope of manufacture,
but are
preferably approximately spherical. Their diameter along their largest spatial
expansion can be
between 0.01 pm (not visually recognizable as capsules) and 10 000 pm
depending on the
components present in their interior and the application. Preference is given
to visible micro-
capsules with a diameter in the range from 100 pm to 7000 pm, in particular
from 400 pm to
5000 pm. The microcapsules are accessible by known methods, with coacervation
and
interfacial polymerization being attributed the greatest importance.
Microcapsules which can be
used are all of the surfactant-stable microcapsules supplied on the market,
for example the
commercial products (the coating material is given in each case in brackets)
Hallcrest
Microcapsules (gelatin, gum arabic), Coletica Thalaspheres (maritime
collagen), Lipotec
Millicapseln (alginic acid, agar agar), Induchem Unispheres (lactose,
microcrystalline cellulose,
hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline
cellulose,
hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid
esters,
phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres
(phospholipids).
Alternatively, it is also possible to use particles which do not have a core-
sheath structure, but in
which the active ingredient is distributed in a matrix of a matrix-forming
material. Such particles
are also referred to as "speckles".
A preferred matrix-forming material is alginate. To produce alginate-based
speckies, an
aqueous alginate solution, which also comprises the active ingredient to be
enclosed or the
active ingredients to be enclosed, is dripped and then hardened in a
precipitating bath
comprising Ca2+ ions or Al3+ ions.
PF 72097 CA 02836849 2013-11-20
Alternatively, instead of alginate, other matrix-forming materials can be
used. Examples of
matrix-forming materials comprise polyethylene glycol, polyvinylpyrrolidone,
polymethacrylate,
polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene
oxide, polyethoxy-
5 oxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, Ficoll
, starch, hydroxyethyl-
cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hyaluronic
acid, carboxy-
methylcellulose, carboxymethylcellulose, deacetylated chitosan, dextran
sulfate and derivatives
of these materials. The matrix formation takes place for these materials for
example via gelling,
polyanion-polycation interactions or polyelectrolyte-metal ion interactions.
The preparation of
10 particles with these matrix-forming materials is known per se.
The particles can be stably dispersed in the aqueous liquid detergents or
cleaners. Stable
means that the compositions are stable at room temperature and at 40 C over a
period of at
least 4 weeks and preferably of at least 6 weeks without the composition
creaming up or
15 sedimenting. The polymers according to the invention bring about,
through the increase in
viscosity, a kinetic slowing of the sedimentation of the particles and thus
their stabilization in the
suspended state.
The release of the active ingredients from the microcapsules or speckies
usually takes place
20 during the application of the compositions comprising them through
decomposition of the sheath
or the matrix as a result of mechanical, thermal, chemical or enzymatic
action.
The branched polyesters with sulfonate groups according to the invention,
which are used in
aqueous textile wash liquors in concentrations between about 1 to about 180
ppm, preferably in
25 concentrations between about 30 to about 90 ppm, bring about an
effective cleaning and soil
release treatment and inhibition of the graying especially for polyester,
polyester/cotton blends
and other synthetic fabrics.
The textile wash liquors are preferably alkaline with a pH range between about
7 to 10 about 11,
in particular between about 7.5 to about 10.5, where typical detergent
ingredients are present.
Surprisingly, especially insofar as the pH and anionic surface-active
compounds are concerned,
the detersive agents usually present in detergents and cleaners are also used
in the cleaners
according to the invention in the amounts as corresponds to the prior art.
They thereby fulfill
their desired purpose, i.e. for example the cleaning or bleaching of fabric,
without having a
disadvantageous effect on the soil release properties of the polyesters with
sulfonate groups
according to the invention. The polyesters with sulfonate groups according to
the invention can
also be used for achieving a soil release finish in standard commercial fabric
softeners for
household use. These comprise essentially softening components, co-softeners,
emulsifiers,
perfumes, dyes and electrolytes, and are adjusted to an acidic pH of less than
7, preferably
between 3 and 5.
The invention further provides a method for producing branched polyesters with
sulfonate
PF 72097 CA 02836849 2013-11-20
26
groups, comprising
1. the reaction of the components A, B, optionally C and optionally D to
give branched
polyesters, where
i. the component A is selected from the group of a,p-olefinically unsaturated
dicarboxylic acids (A2), and
ii. the component B is selected from the group of tri- or higher-functional
alcohols (By),
iii. the optional component C is selected from the group of difunctional
alcohols
(B2) or the difunctional carboxylic acids (C2) without a,p-olefinically
unsaturated bonds,
iv. the optional component D is selected from fatty acids or fatty alcohols,
2. and the subsequent reaction of the branched polyesters obtained in
step a. with hydrogen
sulfite, where the molar amount of hydrogen sulfite is at most 95 mol%, based
on the
amount of a,p-olefinically unsaturated dicarboxylic acid (A2).
Step 1. of the method according to the invention can be carried out without
dilution or in the
presence of a solvent. Suitable solvents are, for example, hydrocarbons such
as paraffins or
aromatics. Particularly suitable paraffins are n-heptane and cyclohexane.
Particularly suitable
aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as
isomer mixture,
ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Also suitable
as solvents
in the absence of acidic catalysts are very particularly ethers, such as, for
example, dioxane or
tetrahydrofuran, and ketones such as, for example, methyl ethyl ketone and
methyl isobutyl
ketone.
According to the invention, the amount of added solvent is at least 0.1% by
weight, based on
the mass of the used starting materials to be reacted, preferably at least 1%
by weight and
particularly preferably at least 10% by weight. It is also possible to use
excesses of solvent,
based on the mass of used starting materials to be reacted, for example 1.01
to 10-fold. Solvent
amounts of more than 100-fold, based on the mass of used starting materials to
be reacted are
not advantageous because at considerably lower concentrations of the
reactants, the reaction
rate diminishes considerably, which leads to uneconomically long reaction
times.
In one preferred embodiment, the reaction is carried out free from solvents.
To carry out step 1. in the method according to the invention, it is possible
to work in the
presence of a water-withdrawing agent as additive, which is added at the start
of the reaction.
PF 72097 CA 02836849 2013-11-20
27
Molecular sieves, in particular molecular sieve 4 A, MgSas and Na2SO4, for
example, are
suitable. During the reaction, further water-withdrawing agent can also be
added, or water-
withdrawing agent can be replaced with fresh water-withdrawing agent. Water
and/or alcohol
formed during the reaction can also be distilled off, and, for example, it is
possible to use a
water separator in which the water is removed with the help of an entrainer.
Step 1. of the method according to the invention can be carried out in the
absence of catalysts.
However, preference is given to working in the presence of at least one
catalyst. These are
preferably acidic inorganic, organometallic or organic catalysts or mixtures
of two or more acidic
inorganic, organometallic or organic catalysts.
Within the context of this specification, acidic catalysts are also considered
to be Lewis acids,
i.e. those compounds according to Rompps Chemie-Lexikon, key word "Acid-base
concept",
which are able to accept an electron pair into the valence shell of one of
their atoms.
For the purposes of the present invention, acidic inorganic catalysts are, for
example, sulfuric
acid, sulfates and hydrogen sulfates, such as sodium hydrogen sulfate,
phosphoric acid,
phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic
silica gel (pH
5 6, in particular 5 5) and acidic aluminum oxide. It is also possible to use,
for example,
aluminum compounds of the general formula Al(0R1)3 and titanates of the
general formula
Ti(0R1)4 as acidic inorganic catalysts, where the radicals R1 can in each case
be identical or
different and are selected independently of one another from
CI-Cm-alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl,
isoamyl, n-hexyl,
isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-
decyl, n-dodecyl,
n-hexadecyl or n-octadecyl.
C3-C12-Cycloalkyl radicals, for example cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl,
cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and
cyclododecyl; preference
being given to cyclopentyl, cyclohexyl and cycloheptyl.
Preferably, the radicals R1 in Al(0R1)3 and Ti(0R1)4 are in each case
identical and selected from
n-butyl, isopropyl, 2-ethylhexyl, n-octyl, decyl or dodecyl.
Preferred acidic organometallic catalysts are selected, for example, from
dialkyltin oxides
R12SnO or dialkyltin diesters R12Sn(0R2)2, where R1 is as defined above and
can be identical or
different.
R2 can have the same meanings as R1 and can additionally be C6-C12-aryl, for
example phenyl,
o-, m- or p-tolyl, xylyl or naphthyl. R2 can in each case be identical or
different.
PF 72097 CA 02836849 2013-11-20
28
Examples of organotin catalysts are tin(II) n-octanoate, tin(II) 2-
ethylhexanoate, tin(II) laurate,
dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, dibutyltin
diacetate, dibutyltin dilaurate,
tibutyltin dimaleate or dioctyltin diacetate. Also conceivable are
organoantimony, organobismuth
or organoaluminum catalysts.
Particularly preferred representatives of acidic organometallic catalysts are
dibutyltin oxide,
diphenyltin oxide and dibutyltin dilaurate.
Preferred acidic organic catalysts are acidic organic compounds with, for
example, phosphate
groups, sulfonic acid groups, sulfate groups or phosphonic acid groups.
Particular preference is
given to sulfonic acids such as, for example, para-toluenesulfonic acid. It is
also possible to use
acidic ion exchangers as acidic organic catalysts, for example polystyrene
resins which contain
sulfonic acid groups and are crosslinked with about 2 mol% of divinylbenzene.
It is also possible to use combinations of two or more of the aforementioned
catalysts. It is
possible as well to use those organic or organometallic or else inorganic
catalysts which are
present in the form of discrete molecules, in immobilized form, for example on
silica gel or on
zeolites.
If it is desired to use acidic inorganic, organometallic or organic catalysts,
then the amount used
is preferably 1 to 10 000 ppm of catalyst, particularly preferably 2 to 5000
ppm, based on the
total mass of the hydroxy- and the carboxy-containing compounds.
If it is desired to use acidic inorganic, organometallic or organic catalysts,
then the method is
carried out in accordance with the invention at temperatures from 60 to 140 C.
Preference is
given to working at temperatures of from 80 to 140 C, particularly preferably
at 100 to 130 C.
According to the invention, it is also possible to use enzymes as catalysts,
although their use is
less preferred.
Enzymes which can be used for this purpose are selected, for example, from
hydrolases
(E.C. 3.-.-.-), and among these particularly from the esterases (E.C. 3.1.-.-
), lipases (E.C.
3.1.1.3), glycosylases (E.C. 3.2.-.-) and proteases (E.C. 3.4.-.-), in free
form or in a form
immobilized physically or chemically on a support, preferably lipases,
esterases or proteases
and particularly preferably esterases (E.C. 3.1.-.-). Very particular
preference is given to
Novozyme 435 (lipase from Candida antarctica B) or lipase from Alcaligenes
sp., Aspergillus
sp., Mucor sp., Penicilium sp., Geotricum sp., Rhizopus sp., Burkholderia sp.,
Candida sp.,
Pseudomonas sp., Thermomyces sp. or porcine pancreas, particular preference
being given to
lipase from Candida antarctica B or from Burkholderia sp. The enzymes listed
are commercially
available, for example from Novozymes Biotech Inc., Denmark.
The enzyme content in the reaction medium is generally in the range from about
0.1 to 10% by
PF 72097 CA 02836849 2013-11-20
29
weight, based on the sum of the components used.
If it is desired to use enzymes as catalysts, then step 1. of the method is
carried out in
accordance with the invention at temperatures of 20 and up to 120 C,
preferably 20 to 100 C
and particularly preferably 20 to 80 C.
The method according to the invention is preferably carried out under inert-
gas atmosphere, i.e.
a gas which is inert under the reaction conditions, for example under carbon
dioxide,
combustion gases, nitrogen or noble gas, among which argon in particular is to
be mentioned.
The pressure conditions of the method according to the invention are generally
not critical. It is
possible to work at significantly reduced pressure, for example at 10 to 500
mbar. The method
according to the invention can also be carried out at pressures above 500
mbar. For reasons of
simplicity, it is preferred to carry out the reaction at atmospheric pressure;
however, it is also
possible to carry it out at a slightly elevated pressure, for example up to
1200 mbar. It is also
possible to work under significantly increased pressure, for example at
pressures up to 10 bar.
Preference is given to carrying out the reaction at reduced pressure or
atmospheric pressure,
particularly preferably at atmospheric pressure.
The reaction time of the method according to the invention is usually 10
minutes to 48 hours,
preferably 30 minutes to 24 hours and particularly preferably 1 to 12 hours.
When the reaction in step 1. is complete, the highly functional branched
polyesters can be
isolated easily, for example by filtering off the catalyst and optionally
stripping off the solvent,
the stripping-off of the solvent usually being carried out at reduced
pressure. Further highly
suitable work-up methods are precipitation of the polymer following the
addition of water and
subsequent washing and drying.
If required, the reaction mixture can be subjected to a decoloration, for
example by treatment
with activated carbon or metal oxides, such as e.g. aluminum oxide, silicon
oxide, magnesium
oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for
example, 0.1 to 50%
by weight, preferably 0.5 to 25% by weight, particularly preferably 1 to 10%
by weight, at
temperatures of, for example, 10 to 140 C, preferably 20 to 130 C and
particularly preferably 30
to 120 C.
This can take place by adding the pulverulent or granular decoloring agent to
the reaction
mixture and subsequent filtration, or by passing the reaction mixture over a
bed of a decoloring
agent in the form of any desired suitable moldings.
The decoloration of the reaction mixture can take place at any desired point
in the work-up
process, for example at the stage of the crude reaction mixture or following
optionally carried
out prewashing, neutralization, washing or solvent removal.
,
PF 72097 CA 02836849 2013-11-20
The reaction mixture can also be subjected to a prewashing and/or a
neutralization and/or a
post-washing, preferably only to a neutralization. Optionally, the order of
neutralization and
prewashing can also be swapped.
5
From the aqueous phase of the washing and/or neutralization it is possible to
recover, at least
partially, any valuable products present by acidification and extraction with
a solvent, and to use
them afresh.
10 In terms of processing, all extraction and washing processes and
apparatuses known per se
can be used for a washing or neutralization in the method according to the
invention, e.g. those
which are described in Ullmann's Encyclopedia of Industrial Chemistry, 6th
ed., 1999 Electronic
Release, Chapter: Liquid-Liquid Extraction - Apparatus. For example, these may
be single-
stage or multi-stage, preferably single-stage, extractions, and also those in
cocurrent or
15 countercurrent operation, preferably countercurrent operation.
However, in a preferred embodiment, it is possible to dispense with a washing,
neutralization
and decoloring.
20 Step 2. of the method according to the invention for the sulfonation of
the polyester can be
carried out without dilution or in the presence of a solvent. Suitable
solvents are, for example,
water or alcohols.
The amount of added solvent according to the invention is at least 0.1% by
weight, based on
25 the mass of the used starting materials to be reacted, preferably at
least 1% by weight and
particularly preferably at least 10% by weight. It is also possible to use
excesses of solvent,
based on the mass of used starting materials to be reacted, for example 1.01
to 10-fold. Solvent
amounts of more than 100-fold, based on the mass of used starting materials to
be reacted, are
not advantageous because, at significantly lower concentrations of the
reactants, the rate of
30 reaction diminishes considerably, which leads to uneconomically long
reaction times.
Step 2. of the method according to the invention is carried out at
temperatures from 60 to
150 C. Preference is given to working at temperatures of from 80 to 120 C,
particularly
preferably at from 90 to 110 C.
Preferably, the polyester is introduced as initial charge as stirable melt at
reaction temperature,
and is then admixed with an aqueous solution of the sulfonating reagent.
Sulfonating reagents which can be used are solutions of the alkali metal or
alkaline earth metal
salts of sulfuric acid (hydrogen sulfites). The concentration of the solutions
is from 10 to 90% by
weight, preferably from 20 to 50% by weight and very particularly preferably
from 30 to 45% by
weight.
PF 72097 CA 02836849 2013-11-20
=
31
Preference is given to using aqueous solutions of sodium hydrogen sulfite,
potassium hydrogen
sulfite or magnesium hydrogen sulfite. Very particular preference is given to
aqueous solutions
of sodium hydrogen sulfite.
Alternatively, it is possible to use an acidic aqueous solution of sodium
thiosulfate, which
disproportionates into hydrogen sulfite.
The reaction time in step 2. of the method according to the invention is
usually 10 minutes to
48 hours, preferably 30 minutes to 24 hours and particularly preferably 1 to 3
hours.
The reaction is complete when hydrogen sulfite can no longer be detected in
the reaction
mixture. During the conversion, the consumption of the hydrogen sulfite in the
reaction mixture
can be monitored qualitatively or quantitatively.
Of suitability for the qualitative monitoring is, for example, the treatment
of a sample of the
reaction mixture with dilute potassium permanganate solution and subsequent
addition of
barium chloride solution. Any hydrogen sulfite present here is firstly
oxidized by permanganate
to sulfate, which, upon contact with barium ions, precipitates out as
sparingly soluble barium
sulfate. It should be taken into consideration that the detection can be
disturbed by the reaction
of the potassium permanganate with maleic acid double bonds.
Of suitability for the quantitative monitoring of the reaction is an
iodometric determination of the
sulfite, as described, for example, in Gerhard Schulze, Jurgen Simon
"Jander/Jahr
Mallanalyse", 17th edition 2009, de Gruyter, Berlin, p. 187.
The present invention makes available branched polyesters with sulfonate
groups which can be
used advantageously for cleaning purposes of textiles while avoiding
redeposition effects.
These polymeric effect substances, which have a low toxicity, can be prepared
by means of a
technically relatively simple and cost-effective method and can be readily
incorporated into
formulations for cleaning purposes in their various presentation forms.
The invention is illustrated in more detail by the examples, without the
examples limiting the
subject matter of the invention.
Examples:
MA = maleic anhydride
TMP = trimethylolpropane
TMP x n PO = reaction product of TMP with
n molar excess of propylene oxide
ASA = octadecenylsuccinic acid
DBTL = dibutyltin dilaurate
Ti(0Bu)4 = titanium tetrabutylate
, PF 72097 CA 02836849 2013-11-20
32
x% NaHS03 means that in the sulfonation reaction precisely the amount of
NaHS03 has been
used which is required to sulfonate x% (of the number) of a,13-olefinically
unsaturated double
bonds theoretically present in the polymer.
The molecular weights of the unsulfonated polyesters were determined by gel
permeation
chromatography (GPC) (column combination: 2 x PLgel 3 jim MIXED-E and 1 x
ResiPore 3 i.tm;
standard: polymethyl methacrylate (PMMA); eluent: THF).
The acid numbers (mg KOH/g polymer) were determined in accordance with DIN
53402.
Polymer 1: MA: TMP x 15.7 PO
98.3 g of MA, 1040.4 g of TMP x 15.7 PO and 0.35 g of Ti(0Bu)4 were weighed
into a 2000 ml
round flask equipped with stirrer, internal thermometer, gas inlet tube and
descending
condenser with capture vessel, and heated to 180 C with stirring. The reaction
mixture was
stirred for 14 h at 180 C while separating off water of reaction until the GPC
control showed a
weight-average molecular weight of 7300 g/mol. The reaction was then completed
by cooling to
room temperature.
The product was obtained in the form of a brown water-insoluble resin.
The following characteristic data were determined:
acid number = 24 mg KOH/g polymer
Mn = 1890 g/mol, Mw = 8390 g/mol
Sulfonation of Polymer 1:
In a round flask, equipped with stirrer, internal thermometer, gas inlet tube
and reflux
condenser, Polymer 1 was admixed with aqueous NaHS03 solution (39% strength),
and the
mixture was heated to 100 C and stirred at this temperature for 5 h. The now
homogeneous
reaction mixture was then cooled to room temperature and adjusted to a pH of
pH = 5 using
50% strength potassium hydroxide solution. The reaction mixture was
transferred to an
aluminum dish and dried by drying in a vacuum drying cabinet (70 C). Brown wax-
like products
were obtained.
Mixture Product
Sulfonated A) Amount of Amount of AN
Color Solubility
polymer NaHS03 Polymer 1
NaHS03 [mg KOH/ g] in water
based [g] (39%
on MA strength in
H20) [g]
la 75% 500.0 84.0 6 Brown
Opaque
lb 50% 105.5 11.7 9 Brown
Opaque
1c 30% 150.0 10.3 8 Brown
Opaque
PF 72097 CA 02836849 2013-11-20
33
Polymer 2: MA: TMP x 15.7 PO
98.5 g of MA, 1051 g of TMP x 15.7 PO and 0.35 g of DBTL were weighed into a
2000 ml round
flask equipped with stirrer, internal thermometer, gas inlet tube and
descending condenser with
capture vessel, and heated to 180 C with stirring. The reaction mixture was
stirred for 10 h at
180 C while separating off water of reaction until the GPC control showed a
weight-average
molecular weight of 9300 g/mol. The reaction was then completed by cooling to
room
temperature.
The product was obtained in the form of a yellow water-insoluble resin.
The following characteristic data were determined:
acid number = 28 mg KOH/g polymer
Mn = 2980 g/mol, Mw = 10 400 g/mol
Sulfonation of Polymer 2:
In a round flask equipped with stirrer, internal thermometer, gas inlet tube
and reflux condenser,
Polymer 2 was admixed with aqueous NaHS03 solution (39% strength), and the
mixture was
heated to 100 C and stirred for 5 h at this temperature. The now homogeneous
reaction mixture
was then cooled to room temperature and adjusted to a pH of pH = 5 using 50%
strength
potassium hydroxide solution. The reaction mixture was transferred to an
aluminum dish and
dried by drying in a vacuum drying cabinet (70 C). Brownish wax-like products
were obtained.
Mixture Product
Sulfonated Amount of Amount of AN
Color Solubility
polymer NaHS03 Polymer 1 NaHS03
[mg KOH/ g] in water
based [9] (39%
on MA strength in
H20) [g]
2a* 90% 500.0 113.0 2 Brownish
Opaque
2b 75% 510.2 89.3 2
Brownish Opaque
* the molecular weight of the sulfonated Polyester 2a was determined by means
of gel permeation
chromatography (GPC) (standard: PMMA; eluent: 0.08 mol/ITRIS-buffer pH = 7.0
in dist water +
0.15 mol/INaCI + 0.01 mo1/1 NaN3): Mn = 5030 g/mol, Mw = 63 800 g/mol.
Polymer 3: MA: TMP x 15.7 PO: ASA
73.6 g of MA, 1042.2 g of TMP x 15.7 PO and 87.2 g of ASA were weighed into a
2000 ml
round flask equipped with stirrer, internal thermometer, gas inlet tube and
descending
condenser with capture vessel, and heated to 180 C with stirring. As a
homogeneous melt was
produced, 0.36 g of DBTL were added as catalyst, and the reaction mixture was
stirred at
160 C while eliminating water of reaction until the GPC control showed a
weight-average
molecular weight of 5700 g/mol. The reaction was then completed by cooling to
room
temperature.
The product was obtained in the form of a brownish water-insoluble resin.
PF 72097 CA 02836849 2013-11-20
34
The following characteristic data were determined:
acid number = 25 mg KOH/g polymer
Mn = 1780 g/mol, Mw = 6310 g/mol
Sulfonation of Polymer 3:
In a round flask equipped with stirrer, internal thermometer, gas inlet tube
and reflux condenser,
Polymer 3 was admixed with aqueous NaHS03 solution (39% strength), and the
mixture was
heated to 100 C and stirred at this temperature for 5 h. The now homogeneous
reaction mixture
was then cooled to room temperature and adjusted to a pH of pH = 5 using 50%
strength
potassium hydroxide solution. The reaction mixture was transferred to an
aluminum dish and
dried by drying in a vacuum drying cabinet (70 C). Orange-colored wax-like
products were
obtained.
Mixture Product
Sulfonated Amount of Amount of AN
Color Solubility
polymer NaHS03 Polymer 1 NaHS03
[mg KOH/ g] in water
based [9] (39%
on MA strength in
H20) [g]
3a 90% 150.3 22.4 16
Orange Opaque
3b 75% 150.0 18.7 12
Orange Opaque
Sulfonated Polymer 4: (MA: TMP x 5.2 PO: ASA) * 75% NaHS03
93.1 g of MA, 453.6 g of TMP x 5.2 PO, 36.7 g of ASA were weighed into a 1000
ml round flask
equipped with stirrer, internal thermometer, gas inlet tube and descending
condenser with
capture vessel and heated to 160 C with stirring. As a homogeneous melt was
formed, 0.18 g of
Ti(n-Bu0)4 was added as catalyst, and the reaction mixture was stirred at 160
C while
separating off water of reaction until the GPC control showed a weight-average
molecular
weight of 9600 g/mol. The reaction mixture was then cooled to 105 C and
admixed with 190 g
of aqueous NaHS03 solution (39% strength). The mixture was then stirred for 5
h at 110 C
before the reaction mixture was cooled to room temperature. The product was
transferred to an
aluminum dish and dried in a vacuum drying cabinet (70 C).
The product was obtained in the form of a yellow, water-soluble wax-like
solid.
The following characteristic data were determined prior to the sulfonation:
acid number = 33 mg KOH/g polymer
Mr, = 1860 g/mol, M = 12 400 g/mol
The following characteristic data were determined:
acid number = 7 mg KOH/g polymer
Polymer 5: MA: TMP x 15.7 PO: PolyTHF 250
49.3 g of MA, 419.1 g of TMP x 15.7 PO and 31.9 g of PolyTHF 250 (technical-
grade, BASF
SE) were weighed into a 1000 ml round flask fitted with stirrer, internal
thermometer, gas inlet
PF 72097 CA 02836849 2013-11-20
tube and descending condenser with capture vessel and heated to 180 C with
stirring. As a
homogeneous melt was formed, 0.15 g of DBTL was added as catalyst and the
reaction mixture
was stirred at 180 C while separating off water of reaction until the GPC
control showed a
weight-average molecular weight of 9600 g/mol. The reaction was then completed
by cooling to
5 room temperature.
The product was obtained in the form of a brownish water-insoluble resin.
The following characteristic data were determined:
acid number = 28 mg KOH/g polymer
Mr, = 1900 g/mol, Mw = 14 800 g/mol
Sulfonation of Polymer 5:
In a round flask equipped with stirrer, internal thermometer, gas inlet tube
and reflux condenser,
Polymer 5 was admixed with aqueous NaHS03 solution (39% strength), and the
mixture was
heated to 100 C and stirred for 5 h at this temperature. The now homogeneous
reaction mixture
was then cooled to room temperature and adjusted to a pH of pH = 5 using 50%
strength
potassium hydroxide solution. The reaction mixture was transferred to an
aluminum dish and
dried by drying in a vacuum drying cabinet (70 C). Yellow wax-like products
were obtained.
Mixture Product
Sulfonated Amount of Amount of AN Color
Solubility
polymer NaHS03 Polymer 1 NaHS03 [mg KOH/ g] in water
based on [g] (39%
MA strength in
H20) [g]
5a 90% 150.0 36.2 19 Yellow Opaque
5b 75% 150.0 30.0 20 Yellow Opaque
Application tests
The specified polymers were added to different liquid detergent formulations
in a concentration
of 5% by weight (see table 1) and tested as to their secondary detergency. The
graying
(redeposition) serves as a quality feature for assessing detergents and
detergent formulations.
This test is used in the development and optimization of detergent
formulations or for assessing
the performance of detergent components.
The graying test consists of three repeat washes, in which, in each cycle,
rinsing is carried out
and fresh soiled fabric is used. The white fabrics are in each case reused and
evaluated at the
end of the experiment.
Washing conditions
Washing device Launder-O-Meter from Atlas, Chicago, USA
PF 72097 CA 02836849 2013-11-20
36
Ca:Mg:NaHCO3 ratio 4:1:8 mol
Washing temperature 40 C
Washing time 30 min (inc. heating time)
Wash cycles 3
Detergent dosing 5.0 g/I
Liquor ratio 1:10
Total liquor 250 ml
Soiled fabric 5 g EMPA 101 cotton fabric with soot/olive
oil soiling
5 g SBL 2004 (soiled ballast fabric, wfk)
White fabric Polyester wft<30A and EMPA 407
Polyamide EMPA 225 and EMPA 406
Ballast fabric cotton, blended fabric
Test fabrics are available, for example, from Wfk-Testgewebe GmbH,
Christenfeld 10, D-41379
Brueggen and from EMPA Testmaterialien AGm Moverstrasse 12, CH-9015 St.
Gallen.
After rinsing, spinning is carried out and the fabric is hung up separately to
dry.
To determine the secondary detergency, the reflectance of the white fabric is
measured before
and after washing using a photometer ((Elrepho) from Datacolor AG, CH-8305
Dietikon,
Switzerland).
The reflectance values are determined at 460 nm, with in each case 4
measurement points
being averaged per fabric type. For comparison, test fabric without the
addition of polymer was
washed. delta R (reflectance of the white fabric washed with polymer addition
minus reflectance
of the white fabric washed with the liquid detergent without polymer) is
evaluated, see table 2.
Table 1
Formulation 1 Formulation 2
20% strength 20% strength
LAS 10.1 7.7
Coconut fatty acid
C12-18
_ _ 2.5 2.4
KOH 3.4 2.7
Lutensol AO 7 5.7 8.6
1,2-Propylene glycol 6 6
Ethanol 2 2
Water ad 90 ad 90
Preparation of the formulations:
LAS, fatty acid, propylene glycol and water are introduced as initial charge,
heated to 40 C and
neutralized with KOH (as 50% strength solution). After cooling, Lutensol AO 7
and ethanol are
added.
PF 72097 CA 02836849 2013-11-
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,
37
Table 2
Washing results in formulations 1 and 2 on PES and PA fabric
Formulation 1 Formulation 2 Formulation 1
Formulation 2
Polyester fabric Polyamide fabric
wfk 30 EMPA EMPA EMPA
EMPA EMPA
A 407 wfk 30 A 407 225 406 225 EMPA
406
delta
Polymer delta R delta R delta R delta R delta R
delta R R delta R
la 7 11 7 8 3 2 2
4
lb 2 7 3 7 2 2 1
2
1c 8 14 6 9 5 4 2
2
3a 6 8 6 9 4 4 2
2
3b 4 9 5 8 2 3 1
3
5a 6 9 6 9 3 3 0
2
5b 6 9 6 9 2 2 0
2
4 3 5 6 4 1 -2 2
3
2b 6 7 8 5 5 3 4
5 ,
2a 6 6 8 4 3 4 3
4
Example relating to formulation stabilities
The specified polymers were added in a concentration of 5% by weight to the
liquid detergent
formulations from table 1 and stored for 2 weeks at 40 C.
No clouding or sediment were evident. Testing the stored samples in a washing
experiment
against a freshly prepared formulation did not give rise to any differences in
the washing
performance.
Texcare SRA-300 F (manufacturer: Clariant GmbH), which can be used as graying
inhibitor for
polyester, could not be stably incorporated under the same conditions into the
specified liquid
detergent formulations; it led to clouding and sediment upon storage.
