Note: Descriptions are shown in the official language in which they were submitted.
,
PF 71736 CA 02836532 2013-11-18
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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 deposit inhibitors in water-conveying systems and as
additive to rinses,
detergents and cleaners, in particular to phosphate-containing and phosphate-
free cleaner
formulations for machine dishwashing.
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 Al. These branched copolyesters are
suitable, according
to DE 26 21 653 Al, 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 Al describes hair treatment compositions with a content of water-
soluble or
-dispersible branched copolyesters comprising sulfonate groups.
DE 26 37 926 Al describes water-soluble or -dispersible and branched
copolyesters comprising
sulfonate groups with an application spectrum comparable to DE 26 21 653 Al.
US 5,281,630 describes a prepolymer based on a terephthalic polymer, glycol
and oxyalkylated
polyol, which is reacted with a,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 Al 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.
PF 71736 CA 02836532 2013-11-18
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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.
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. lrrgang.
Polymers of carboxyl-group-containing and/or sulfonic acid-group-containing
monomers
obtainable by radical polymerization have been an important constituent of
phosphate-
containing and phosphate-free machine dishwashing detergents for some years.
As a result of
their soil-dispersing and deposit-inhibiting effect, they make a considerable
contribution to the
cleaning and clear-rinse performance of machine dishwashing detergents. They
ensure that no
salt deposits of the hardness-forming calcium and magnesium ions remain on the
ware.
Copolymers of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid are
often used for
this purpose.
These polymers are also used in water-conveying systems as agents for
preventing mineral
deposits such as e.g. calcium and magnesium sulfate, magnesium hydroxide,
calcium and
barium sulfate and calcium phosphate on heat-transfer areas or in pipelines.
Water-conveying
systems to be mentioned here are, inter alia, cooling and boiler-feed water
systems and
industrial process waters. However, these polymers are also used as deposit
inhibitors in
seawater desalination by distillation and by membrane processes such as
reverse osmosis or
electrodialysis.
A disadvantage of these polymers of carboxyl-group-containing and/or sulfonic
acid-group-
containing monomers obtainable by radical polymerization is that they are not
biodegradable.
Biodegradable polymers such as, for example, polyaspartic acid, however, have
proven to be
not really commercially acceptable on account of high production costs.
It was therefore the object of the invention to provide substances which can
be used for
cleaning purposes, in particular as additive to phosphate-containing and
phosphate-free cleaner
formulations for machine dishwashing, and for the purpose of deposit
inhibition in water-
conveying systems, and which are readily biodegradable. 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 and good biodegradability. 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
,
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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
i. the component A is selected from the group of a,3-olefinically unsaturated
dicarboxylic acids (A2), and
ii. the component B is selected from the group of di- or higher-functional
alcohols (By),
iii. the optional component C is selected from the group of di- or higher-
functional carboxylic acids (AO and hydroxycarboxylic acids (AB) without
cc, f3-olefinically unsaturated bonds,
iv. the optional component D is selected from the compounds of the formula
CH3(-0-CH2-CH2)n-OH, where n corresponds to an integer from the range
from 2 to 40,
with the proviso that
if only difunctional alcohols (B2) are selected as component B, the component
C is
present in the reaction (a.) and is selected from the group of tri- or higher-
functional
carboxylic acids (Ax) and tri- or higher-functional hydroxycarboxylic acids
(AB) without
a,[3-olefinically unsaturated bonds
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,f3-olefinically unsaturated dicarboxylic acid (A2).
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 (AO of component C carry no sulfonic acid or sulfonate
groups.
,
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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 (aá a rule a small molecule with
a plurality of
reactive end groups), onto which, through a constantly repeating controlled
reaction sequence,
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,
Z is the average number of monomer units forming branches,
L 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%.
PF 71736 CA 02836532 2013-11-18
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
5 (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
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.
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. Very
particular
preference is given here to using less than 10 mol% of component D.
Preferably, component D
is selected from the compounds of the formula CH3(-0-CH2-CH2)n-OH, where n
corresponds to
an integer from the range from 2 to 30, particularly preferably from 2 to 25.
In a further preferred embodiment of the branched polyesters with sulfonate
groups, in step a.
the fraction of the tri- or higher-functional components B and/or C in the
mixture with the
difunctional components B and/or C is from 50 to 100 mol%, preferably from 70
to 100 mol%
and very particularly preferably from 80 to 100 mol%, based on the total
amount of components
B and/or C.
In a further preferred embodiment of the branched polyesters with sulfonate
groups, in step a.
the fraction of the tri- or higher-functional components B and/or C 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 30 mol% of components B and, if present, C are tri- or higher-
functional, based on the
total amount of components A, B, C and D. Preferably, in this connection, at
least 35 mol%,
particularly preferably 40 mol% and in particular at least 45 mol%, of the
components B and, if
present, C are tri- or higher-functional. Preferably, the fraction of the tri-
or higher-functional
components B and, if present, C, based on the total amount of components A, B,
C and D, is at
PF 71736 CA 02836532 2013-11-18
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most 90 mol%, preferably at most 80 mol%, very preferably at most 75 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 50 mol%,
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,13-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
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 (Mw) 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,13-
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.
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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-C1-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 C1-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-C1-C4-alkyl
esters and very
particular preference being given to the anhydrides.
Within the context of this specification, C1-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.
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.
For the branched polyesters with sulfonate groups as difunctional alcohols
(By=B2), 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-
did, 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-ethyl-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 or polypropylene glycols HO(CH[CH3]CH20)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, polyethylene polypropylene glycols, where the order
of the ethylene
oxide of the propylene oxide units can be blockwise or random,
or polytetramethylene glycols, poly-1,3-propanediols or polycaprolactones with
a molecular
PF 71736 CA 02836532 2013-11-18
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weight of up to 5000 g/mol, preferably with a molecular weight up to 2000
g/mol.
As difunctional alcohols (By=B2), particular preference is given here to using
ethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,3- and 1,4-
bis(hydroxymethyl)cyclohexane,
diethylene glycol, triethylene glycol,
or polyethylene glycols having an average molecular weight between 200 and
1000 g/mol.
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(hydroxypropy1)-
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,
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 ethylene oxide.
Within the context of the present invention, it is also possible to use a
mixture of di- or higher-
functional alcohols (By).
,
PF 71736 CA 02836532 2013-11-18
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9
For the branched polyesters with sulfonate groups, the di- or higher-
functional carboxylic acids
(Ax) without a,3-olefinically unsaturated bonds preferably 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
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
where the specified dicarboxylic acids can also be substituted, for example by
C1-C20-alkyl
groups or C2-C20-alkenyl groups,
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-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, 3,3-
dimethylglutaric acid,
dodecenylsuccinic acid, hexadecenylsuccinic acid, octadecenylsuccinic acid,
Furthermore, for the branched polyesters with sulfonate groups, the di- or
higher-functional
carboxylic acids (Ax) without a,3-olefinically unsaturated bonds which can be
used are
trimellitic acid and its derivatives, for example its anhydrides and/or ester
derivatives,
or pyromellitic acid and its derivatives, for example its anhydrides and/or
ester derivatives.
The di- or higher-functional carboxylic acids (Ax) 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 C1-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-C1-C4-alkyl
esters and very
particularly preferably being given to the anhydrides.
PF 71736 CA 02836532 2013-11-18
For the branched polyesters with sulfonate groups as di- or higher-functional
carboxylic acids
(Ax) without a43-olefinically unsaturated bonds, particular preference is
given to using
5 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.
10 Within the context of the present invention, it is also possible to use
a mixture of di- or higher-
functional carboxylic acids (Ax) without a,p-olefinically unsaturated bonds.
For the branched polyesters with sulfonate groups as hydroxycarboxylic acids
(AxBy) without
a,I3-olefinically unsaturated bonds, preference is given to using
citric acid, the hydrates of citric acid, such as e.g. citric acid
monohydrate, hydroxyacetic acid,
hydroxypropionic acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric
acid, isocitric acid,
dimethylolpropionic acid or dimethylolbutyric acid.
Particular preference is given to using citric acid, its hydrates or tartaric
acid.
Within the context of the present invention, it is also possible to use a
mixture of
hydroxycarboxylic acids (AB).
In a preferred embodiment, the branched polyesters with sulfonate groups are
based on a
number of different components A, B and C, which is less than or equal to 4,
i.e. in step a. 4 or
fewer different components A, B and C are used. Preferably, the number of
different
components A, B and C is 3. The number of different components A, B and C is
of course at
least 2.
In a further preferred embodiment, 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 cleaners, rinses or detergents or mixtures for
water treatment.
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.
PF 71736 CA 02836532 2013-11-18
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In this connection, mention is to be made of solid formulations such as
powders, tablets and
liquid formulations.
The invention therefore further provides the use of the branched polyesters
with sulfonate
groups according to the invention, or mixtures thereof in rinses, cleaners or
detergents, in
particular in dishwashing detergents.
They can be used particularly advantageously in machine dishwashing
detergents. They are
characterized here in particular by their deposit-inhibiting effect both
towards inorganic and also
organic deposits. In particular, they inhibit deposits of calcium and
magnesium carbonate and
calcium and magnesium phosphates and phosphonates. Additionally, they prevent
deposits
which originate from the dirt constituents of the wash liquor, such as grease,
protein and starch
deposits.
The machine cleaning formulations according to the invention can be provided
in liquid or solid
form, in single-phase or multi-phase, as tablets or in the form of other
metering units, in
packaged or unpackaged form.
The polymers can be used either in multicomponent product systems (separate
use of cleaner,
rinse aid and regenerating salt), and also in those dishwashing detergents in
which the
functions of cleaner, rinse aid and regenerating salt are combined in one
product (3-in-one
products, 6-in-one products, 9-in-one products, all-in-one products).
A preferred embodiment of the mixtures according to the invention is given by
a cleaning
formulation for machine dishwashing comprising, as components:
a) 1 to 20% by weight of at least one polymer according to the invention
b) 0 to 50% by weight of complexing agents,
c) 0 to 70% by weight of phosphates,
d) 0 to 60% by weight of further builders and cobuilders,
e) 0.1 to 20% by weight of nonionic surfactants,
f) 0.1 to 30% by weight of bleaches and optionally bleach activators,
g) 0 to 8% by weight of enzymes,
h) 0 to 50% by weight of one or more further additives such as anionic or
zwitterionic
surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors,
antifoams, dyes,
fragrances, fillers, organic solvents, tableting auxiliaries, disintegrants,
thickeners,
solubility promoters and water,
the sum of the components from a) to h) giving 100% by weight.
A detailed description of components b) to h) can be found in WO 2008/13213 Al
and in
DE 2007 006630 Al.
,
PF 71736 CA 02836532 2013-11-18
12
The components b) to h) are known to the person skilled in the art from the
prior art and are
described in general in WO 2008/13213 Al and in DE 2007 006630 Al. Suitable
complexing
agents b) are described, for example, in WO 2008/13213 Al pp. 24-26. The
phosphates c) used
are, for example, the substances described in WO 2008/13213 Al pp. 18-21.
Builders and
cobuilders d) are understood, for example, as meaning the substances described
in
WO 2008/13213 Al pp. 21-24 and in DE 2007 006630 Al pp. 5-7. Suitable nonionic
surfactants
e) can be found by the person skilled in the art for example in DE 2007 006630
Al pp. 9-12.
Bleaches and bleach activators f) are well known to the person skilled in the
art, for example
from WO 2008/13213 Al pp. 29-31. Examples of enzymes g) are described in WO
2008/13213
Al pp. 26-29. 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 invention further provides the use of the branched polyesters with
sulfonate groups
according to the invention, or mixtures thereof, as deposit inhibitors in
water-conveying
systems.
Water-conveying systems in which the polymers according to the invention can
be used are, in
particular, seawater desalination plants, cooling water systems and boiler-
feed water systems
and industrial process waters.
In general, the polymers according to the invention are added to the water-
conveying systems
in amounts of from 0.1 mg/I to 100 mg/I. The optimum dosing is governed by the
requirements
of the particular application and/or by the operating conditions of the
particular process. For
example, in the case of thermal seawater desalination, the polymers are
preferably used in
concentrations of 0.5 mg/I to 10 mg/I. In industrial cooling circulations or
boiler-feed water
systems, polymer concentrations up to 100 mg/I are used. Water analyses are
often carried out
in order to ascertain the proportion of deposit-forming salts and thus the
optimum dosing.
Formulations which, besides the polymers according to the invention, and
depending on
requirements, can comprise inter alia phosphonates, polyphosphates, zinc
salts, molybdate
salts, organic corrosion inhibitors such as benzotriazole, tolyltriazole,
benzimidazole or
ethynylcarbinol alkoxylates, biocides, complexing agents and/or surfactants,
can also be added
to the water-conveying systems. Examples of phosphonates are 1-hydroxyethane-
1,1-diphosphonic acid (HEDP), 2-phosphonobutane-1,2,4-tricarboxylic acid
(PBTC),
aminotrimethylenephosphonic acid (ATMP),
diethylenetriaminepenta(methylenephosphonic
acid) (DTPMP) and ethylenediaminetetra(methylenephosphonic acid) (EDTMP),
which are used
in each case in acid form or in the form of their sodium salts.
The invention further provides a method for producing branched polyesters with
sulfonate
groups, comprising the
PF 71736 CA 02836532 2013-11-18
13
1. 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,[3-olefinically unsaturated
dicarboxylic acids (A2), and
ii. the component B is selected from the group of di- or higher-functional
alcohols (By),
iii. the optional component C is selected from the group of di- or higher-
functional carboxylic acids (AO and hydroxycarboxylic acids (AB) without
a,3-olefinically unsaturated bonds,
iv. the optional component D is selected from the compounds of the formula
CH3(-0-CH2-CH2)n-OH, where n corresponds to an integer from the range
from 2 to 40,
with the proviso that
if only difunctional alcohols (B2) are selected as component B, the component
C is
present in the reaction (a.) and is selected from the group of tri- or higher-
functional carboxylic acids (A.) and hydroxycarboxylic acids (AB) without
a,6-olefinically unsaturated bonds,
2. 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,6-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.
PF 71736 CA 02836532 2013-11-18
14
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.
Molecular sieves, in particular molecular sieve 4A, MgSO4 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
Cl-C20-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
PF 71736 CA 02836532 2013-11-18
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.
5
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 mor/o 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.G. 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.,
PF 71736 CA 02836532 2013-11-18
16
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
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.
If it is desired to use citric acid or sugar compounds and derivatives thereof
in the
polycondensation reaction, the reaction is carried out at temperatures of 60
to 140 C.
Preference is given to working at temperatures of 80 to 130 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
PF 71736 CA 02836532 2013-11-18
17
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.
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.
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.
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
countercurrent operation, preferably countercurrent operation.
However, in a preferred embodiment, it is possible to dispense with a washing,
neutralization
and decoloring.
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
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
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
PF 71736 CA 02836532 2013-11-18
18
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.
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
Maflanalyse", 17th edition 2009, de Gruyter, Berlin, p. 187.
The present invention makes available branched polyesters with sulfonate
groups which, even
on account of the high density of carboxylic acids, carboxylates and/or
sulfonates, can be used
for cleaning purposes and for water treatment purposes and which are
nevertheless readily
biodegradable. 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
,
PF 71736 CA 02836532 2013-11-18
,
19
subject matter of the invention.
Examples:
MA = maleic anhydride
TMP = trimethylolpropane
TMP x n EO = reaction product of TMP with
n molar excess of ethylene oxide
ASA = octadecenylsuccinic acid
CA = citric acid monohydrate
DBTL = dibutyltin dilau rate
Ti(0Bu).4 = titanium tetrabutylate
*x% NaHS03 means that in the sulfonation reaction the amount of NaHS03 has
been used
which is required to sulfonate x% 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 I.Lrn MIXED-E and 1 x
ResiPore 3 ilm;
standard: polymethyl methacrylate (PMMA); eluent: THF).
The acid numbers (mg KOH/g polymer) were determined in accordance with DIN
53402.
Example 1:
Polymer 1: MA: TMP x 12 EO
44.7 g of MA and 255.2 g of TMP x 12 EO were weighed into a 500 ml round flask
equipped
with stirrer, internal thermometer, gas inlet tube and descending condenser
with capture vessel,
and heated to 160 C with stirring until a homogeneous melt had formed. Then,
0.1 g of DBTL
was added and the reaction mixture was stirred for 8 h at 160 C while
separating off water of
reaction until the GPC control showed a weight-average molecular weight of
6900 g/mol. The
reaction was then completed by cooling to room temperature.
The product was obtained in the form of a yellow water-soluble resin.
The following characteristic data were determined:
acid number = 47 mg KOH/g polymer
Mn = 1660 g/mol, Mõõ = 8740 g/mol
Sulfonated Polymer la: (MSA: TMP x 12 EO) *25% NaHS03
150 g of Polymer 1 and 15.3 g of aqueous NaHS03 solution (39% strength) were
weighed into a
500 ml round flask equipped with stirrer, internal thermometer, gas inlet tube
and reflux
condenser, heated to 100 C with stirring and held at the temperature until the
hydrogen sulfite
detection in the reaction mixture was negative. The reaction mixture was then
cooled to room
,
PF 71736 CA 02836532 2013-11-18
temperature and adjusted to a pH of pH = 7 using 50% strength aqueous
potassium hydroxide
solution. The reaction mixture was transferred to an aluminum dish and dried
by drying in a
vacuum drying cabinet (70 C).
The product was obtained in the form of a yellow water-soluble resin.
5 The following characteristic data were determined:
acid number = 8 mg KOH/g polymer
Example 2:
10 Polymer 2: MA: TMP x 12 EO: ASA
137 g of MA, 491.4 g of ASA and 1875.7 g TMP x 12 EO were weighed into a 500
ml round
flask equipped with stirrer, internal thermometer, gas inlet tube and
descending condenser with
capture vessel, and heated to 170 C with stirring until a homogeneous melt had
formed. Then,
0.75 g of Ti(0Bu)4 was added and the reaction mixture was stirred for 11 h at
170-180 C while
15 separating off water of reaction until the GPC control showed a weight-
average molecular
weight of 5900 g/mol. The reaction was then completed by cooling to room
temperature.
The product was obtained in the form of a yellowish water-insoluble resin.
The following characteristic data were determined:
acid number = 33 mg KOH/g polymer
20 Mn = 650 g/mol, M,,,, = 6400 g/mol
Sulfonated Polymer 2a: (MA: TMP x 12 EO: ASA)* 25% NaHS03
1001 g of Polymer 2 and 77.3 g of aqueous NaHS03 solution (39% strength) were
weighed into
a 2000 ml round flask equipped with stirrer, internal thermometer, gas inlet
tube and reflux
condenser, heated to 100 C with stirring and held at the temperature until the
hydrogen sulfite
detection in the reaction mixture was negative. The reaction mixture was then
cooled to room
temperature and adjusted to a pH of pH = 7 using 50% strength aqueous
potassium hydroxide
solution. The reaction mixture was transferred to an aluminum dish and dried
by drying in a
vacuum drying cabinet (70 C).
The product was obtained in the form of a yellow water-soluble and wax-like
solid.
The following characteristic data were determined:
acid number = 16 mg KOH/g polymer
Example 3:
Polymer 3: CA: MA: TMP
68.8 g of MA, 443 g of CA and 189.1 g of TMP 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 130 C with stirring until a homogeneous melt had
formed. Then,
0.21 g of Ti(0Bu)4 was added and the reaction mixture was stirred for 3 h at
130 C while
separating off water of reaction until the GPC control showed a weight-average
molecular
weight of 6400 g/mol. The reaction was then completed by cooling to room
temperature.
PF 71736 CA 02836532 2013-11-18
21
The product was obtained in the form of a colorless water-insoluble amorphous
solid.
The following characteristic data were determined:
acid number = 367 mg KOH/g polymer
Mn 120 g/mol, Mw = 9760 g/mol
Sulfonated Polymer 3a: (CA: MA: IMP) * 30% NaHS03:
150 g of Polymer 3 and 12 g of aqueous NaHS03 solution (39% strength) were
weighed into a
250 ml round flask equipped with stirrer, internal thermometer, gas inlet tube
and reflux
condenser, heated to 100 C with stirring and stirred for 5 h at this
temperature. The reaction
mixture was then cooled to room temperature and adjusted to a pH of pH = 5
using 50%
strength aqueous potassium hydroxide solution. The reaction mixture was
transferred to an
aluminum dish and dried by drying in a vacuum drying cabinet (70 C).
The product was obtained in the form of a yellow water-soluble and wax-like
solid.
Sulfonated Polymer 3b: (CA: MA: TMP)* 60% NaHS03
100 g of Polymer 3 and 16 g of aqueous NaHS03 solution (39% strength) were
weighed into a
250 ml round flask equipped with stirrer, internal thermometer, gas inlet tube
and reflux
condenser, heated to 100 C with stirring and stirred for 5 h at this
temperature. The reaction
mixture was then cooled to room temperature and adjusted to a pH of pH = 5
using 50%
strength aqueous potassium hydroxide solution. The reaction mixture was
transferred to an
aluminum dish and dried by drying in a vacuum drying cabinet (70 C).
The product was obtained in the form of a yellow water-soluble and wax-like
solid.
Sulfonated Polymer 3c: (CA: MA: TMP) * 90% NaHS03
1008 g of Polymer 3 and 24 g of aqueous NaHS03 solution (39% strength) were
weighed into a
2000 ml round flask equipped with stirrer, internal thermometer, gas inlet
tube and reflux
condenser, heated to 100 C with stirring and stirred for 5 h at this
temperature. The reaction
mixture was then cooled to room temperature and adjusted to a pH of pH = 5
using 50%
strength aqueous potassium hydroxide solution. The reaction mixture was
transferred to an
aluminum dish and dried by drying in a vacuum drying cabinet (70 C).
The product was obtained in the form of a yellow water-soluble and wax-like
solid.
Example 4: Calcium carbonate - inhibition test
A solution of NaHCO3, Mg2SO4, CaCl2 and polymer is shaken for 2 h at 70 C in a
water bath.
After filtering the still-warm solution through a 0.45 pm Milex filter, the Ca
content of the filtrate
is determined by complexometry or by means of a Ca2+-selective electrode and,
by means of a
before/after comparison, the CaCO3 inhibition is determined in % (see formula
I).
PF 71736 CA 02836532 2013-11-18
22
Ca2+ 215 mg/I
mg2. 43 mg/I
HCO3- 1220 mg/I
Na + 460 mg/I
Cl- 380 mg/I
S042- 170 mg/I
Polymer 10 mg/I
Temperature 70 C
Time 2 hours
pH 8.0-8.5
CaCO3 inhibition (%) = mg (Ca2+) after 24 h ¨ mg (Ca2+) blank value after 24
h/mg (Ca2+) zero
value ¨ mg (Ca 21 blank value after 24 h x 100
Table 1
Inhibition [%]
Example
1 40.8
la 49.2
2 47.5
2a 61.5
3 35.8
3a 44.8
3b 52.3
3c 59.8
The polymers were tested in the following phosphate-free formulations PF1 and
PF2, and also
in the phosphate-based formulation P1. The composition of the polymers is
shown in Table 3
(data in % by weight).
Table 2
PF 1 PF 2 P1
Protease 1 1 1
Amylase 0.2 0.2 0.2
Nonionic surfactant 5 5 3
Polymer 10 10 6.5
Sodium percarbonate 10.5 10.5 14
Tetraacetylethylenediamine 4 4 4
Sodium disilicate 2 2 2
Sodium tripolyphosphate 50
Sodium carbonate 18.8 18.8 18.8
PF 71736 CA 02836532 2013-11-18
23
Sodium citrate dihydrate 33 48 .
Methylglycinediacetic acid 15 0
Hydroxyethane-(1,1-diphosphonic acid) 0.5 0.5 0.5
Data in % by weight based on the total amount of all components
Here, the following experimental conditions were observed:
Dishwasher: Miele G 1222 SCL
Program: 65 C (with prewash)
Ware: 3 knives (WMF Tafelmesser Berlin, monoblock)
3 drinking glasses Amsterdam 0.2 I
3 BREAKFAST PLATES "OCEAN BLUE" (melamine)
3 porcelain plates: RIMMED PLATES FLAT 19 cm
Arrangement: Knives in the cutlery drawer, glasses in the upper basket,
plates in the lower
basket
Dishwashing detergent: 21 g
Addition of soiling: 50 g of ballast soiling is defrosted and metered in with
the formulation after
the prewash; for composition see below
Clear-rinse temperature: 65 C
Water hardness: 21 German hardness (Ca/Mg):HCO3 (3:1):1.35
Wash cycles: 15; break in between for 1 h in each case (10 min with door open,
50 min with
door closed)
Evaluation: Visually after 15 wash cycles
The evaluation of the ware was carried out after 15 cycles in a darkened
chamber under light
behind an apertured diaphragm.
Composition of the ballast soiling:
Starch: 0.5% potato starch, 2.5% gravy
Grease: 10.2% margarine
Protein: 5.1% egg yolk, 5.1% milk
Others: 2.5% tomato ketchup, 2.5% mustard, 0.1% benzoic acid, 71.4% water
Result:
The formulations with polymer are characterized in particular by their very
high deposit-inhibiting
effect towards inorganic and organic deposits on glass, knives, porcelain and
plastic parts.
Furthermore, they increase the cleaning power of the dishwashing detergent and
favor the run-
off of the water from the ware, so that particularly clear glasses and shiny
metal cutlery items
are obtained.
