Note: Descriptions are shown in the official language in which they were submitted.
CA 02879574 2015-01-20
PF73489
As originally filed
1
Use of branched polyesters based on citric acid as additive in washing
compositions,
cleaners, detergents or a formulation for water treatment
The present invention relates to the use of branched polyesters obtainable by
polycondensation of citric acid with at least one polyalcohol, and optionally
with
polycarboxylic acid component as additive in washing compositions, cleaners,
detergents or a formulation for water treatment and to mixtures comprising
such
branched polyesters. The invention further relates to the use of
hydrophobically
modified branched polyesters, and to the method for cleaning, washing or water
treatment using such branched polyesters.
WO 93/22362 describes a process for preparing polyesters from citric acid and
polyhydroxyl compounds and their use as additive to low-phosphate or phosphate-
free
detergents and cleaners. The polyhydroxyl compounds are oligo- and
polysaccharides,
modified oligo- and polysaccharides, and polyvinyl alcohols.
US 5,652,330 describes polycondensates of citric acid which are either
polycondensates of citric acid with itself or into which alcohol components
are
condensed in deficiency with a molar ratio of 100:1 to 2.5:1. The
polycondensates
described therein are used in detergents and cleaners especially for
preventing scale
deposits.
WO 2012/028496 describes branched polyesters which comprise citric acid as
structural component, processes for preparing such polyesters, and their use
for
solubilizing sparingly soluble, basic pharmaceutical active ingredients.
WO 92/16493 claims citric acid esters of polyhydroxyl compounds such as
polyglycerol
or sugar alcohols and their use in detergents and cleaners.
Polymers obtainable by free-radical polymerization and composed of carboxyl-
group-
containing and/or sulfonic acid-group-containing monomers have been an
important
constituent of phosphate-containing and phosphate-free machine dishwashing
detergents for many years. By virtue of their soil-dispersing and deposit-
inhibiting
effect, they make a considerable contribution to the cleaning and rinsing
performance
of machine dishwashing compositions. For instance, they ensure that no salt
deposits
of the hardness-forming calcium and magnesium ions remain on the ware.
as originally filed"
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2
Homopolymers of acrylic acid or 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 surfaces 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 scale inhibitors in the desalination of seawater or brackish
water by
distillation and by membrane processes such as reverse osmosis or
electrodialysis.
One disadvantage of these polymers obtainable by free-radical polymerization
and
composed of carboxyl-group-containing and/or sulfonic acid-group-containing
monomers is that they are not biodegradable. Biodegradable polymers such as,
for
example, polyaspartic acid, however, have struggled to gain acceptance
commercially
due to the 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
scale
inhibition in water-conveying systems, and are biodegradable. It was a further
object of
the invention to provide substances which can be readily incorporated into
formulations
for cleaning purposes in their various presentation forms.
These and other objects are achieved, as is evident from the disclosure of the
present
invention, by the various embodiments of the invention, in particular by the
use of
branched polyesters obtainable by polycondensation of
a. citric acid (component A) with
b. at least one polyalcohol (component B) and
c. optionally a polycarboxylic acid component (component C) and
optionally reaction with
d. at least one component D selected from the group consisting of: C6-C30
alkyl- or alkenylcarboxylic acids, 06-030 alkyl or alkenyl alcohols, 06-030
alkyl- or alkenylamines, 06-030 aliphatic isocyanates during the
polycondensation or subsequently
,,as originally filed"
CA 02879574 2015-01-20
P F73489
,
3
as additive in washing compositions, cleaners, detergents or a formulation for
water
treatment.
The molar ratio of citric acid to polyalcohol is 5.0:1.0 to 1.0:1.5.
Preferably, the molar
ratio of citric acid to polyalcohol is 3.5:1 to 1.0:1.5.
In a further preferred embodiment of the process according to the invention,
hydrophobically modified branched polyesters are used.
Within the context of the present invention, hydrophobically modified branched
polyesters are understood as meaning modified polyesters of citric acid and at
least
one polyhydroxyl compound and optionally one polycarboxylic acid in which the
accessible hydroxyl and/or carboxyl groups have at least partially been
further
modified, i.e. have been reacted with reagents which alter the properties of
the
polyesters modified in this way. Properties in this connection are solubility,
dispersibility
and hydrophobicity.
The modification of the polyester preferably takes place with the polyesters
according
to the invention of citric acid and polyhydroxyl compounds, as are described
above.
Hydrophobically modified branched polyesters of citric acid and polyhydroxyl
compounds can be obtained by adding alkyl- or alkenylcarboxylic acids, alkyl
or alkenyl
alcohols, alkyl- or alkenylamines and/or aliphatic isocyanates during the
condensation
reaction or by means of a subsequent reaction.
The hydrophobically modified polyesters have proven to be advantageous for
cleaning
ware items heavily soiled with domestic fats. In addition, they can be
converted easily
into solid forms. In particular, the production of granules is facilitated by
the
hydrophobicization step.
Particular preference is given to the use of hydrophobically modified branched
polyesters which are obtained by adding alkyl- or alkenylcarboxylic acids
during the
condensation reaction or in a subsequent reaction step.
In order to achieve an amphiphilic character, the highly functional, highly
branched
polyesters of citric acid and polyhydroxyl compounds (during the condensation
reaction
,,as originally filed"
CA 02879574 2015-01-20
PF73489
,
. 4
or subsequently) can also be reacted with hydrophobic and hydrophilic agents,
for
example with long-chain alkyl- or alkenylcarboxylic acids, alkyl or alkenyl
alcohols,
alkyl- or alkenylamines or isocyanates and simultaneously with mono-, di- or
higher-
functional alcohols, amines, acids or isocyanates having polyethylene glycol
chains.
Hyperbranched polyesters are preferably suitable. Within the context of this
invention,
hyperbranched polyesters are understood as meaning uncrosslinked polyesters
with
hydroxyl and carboxyl 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 via the insoluble fraction of the polymer, is present.
Hyperbranched polyesters can on the one hand be formed starting from a central
molecule analogously to dendrimers, but with nonuniform chain length of the
branches.
On the other hand, they can also have a linear structure, with functional side
groups, or
else, being a combination of the two extremes, have linear and branched
molecular
moieties. For the definition of dendrimers 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.
In connection with the present invention, "hyperbranched" is understood as
meaning
that the degree of branching (DB) is 10 to 99.9%, preferably 20 to 99%,
particularly
preferably 20- 95%. The degree of branching DB is defined here as DB CYO = (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 linearly bonded monomer units.
In connection with the present invention, "dendrimeric" is understood as
meaning that
the degree of branching is 99.9-100%. For the definition of the "Degree of
Branching",
see H. Frey et al., Acta Polym. 1997, 48, 30-35.
Component A
,,as originally filed"
CA 02879574 2015-01-20
P F73489
According to the invention, citric acid is understood as meaning citric acid
anhydrate
and also the hydrates of citric acid, such as, for example, citric acid
monohydrate.
Component B
5
According to the invention, suitable polyalcohols are alcohols with at least
two hydroxyl
groups and up to six hydroxyl groups. Preferably, diols or triols or mixtures
of different
diols and/or triols are contemplated. Suitable polyalcohols are, for example,
polyetherols. The polyetherols can be obtained by reaction with ethylene
oxide,
propylene oxide and/or butylene oxide. In particular, polyetherols based on
ethylene
oxide and/or propylene oxide are suitable. It is also possible to use mixtures
of such
polyetherols.
Suitable diols are, for example 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-decandiol, 1,10-decandiol, 1,2-dodecandiol, 1,12-dodecandiol,
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)-methy1-2,4-
pentanediol, 2,4-dimethy1-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-
dimethy1-2,5-
hexanediol, 2,2,4-trimethy1-1,3-pentanediol, pinacol, diethylene glycol,
triethylene
glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols
HO(CH2CH20)n-H or
polypropylene glycols HO(CH[CH3]CH20)0-H, where n is an integer and n ?. 4,
polyethylene polypropylene glycols, where the sequence of the ethylene oxide
of the
propylene oxide units can be blockwise or random, polytetramethylene glycols,
preferably up to a molecular weight up to 5000 g/mol, poly-1,3-propanediols,
preferably
with a molecular weight up to 5000 g/mol, polycaprolactones or mixtures of two
or more
representatives of the above compounds. For example, one to six, preferably
one to
four, particularly preferably one to three, very particularly preferably one
to two and in
particular one diol can be used. Here, one or both hydroxyl groups in the
diols specified
above can be substituted by SH groups. Diols preferably used are ethylene
glycol, 1,2-
propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
1,8-
octanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-
õas originally filed÷
CA 02879574 2015-01-20
PF73489
6
bis(hydroxymethyl)cyclohexane, and diethylene glycol, triethylene glycol,
dipropylene
glycol, tripropylene glycol and polyethylene glycols with an average molecular
weight
between 200 and 1000 g/mol.
The dihydric polyalcohols can optionally also comprise further functionalities
such as,
for example, carbonyl, carboxyl, alkoxycarbonyl or sulfonyl, such as, for
example,
dimethylolpropionic acid or dimethylolbutyric acid, and C1-C4-alkyl esters
thereof,
although the alcohols preferably have no further functionalities.
Preferred diols are ethylene glycol, diethylene glycol and polyethylene glycol
with an
average molecular weight between 200 and 1000 g/mol.
Suitable triols or higher-functional polyalcohols are, for example, 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 (THE IC), tris(hydroxypropyl) isocyanurate and
N-[1,3-
bis(hydroxymethyl)-2,5-dioxo-4-imidazolidiny1]-N,N'-bis(hydroxymethyOurea.
Preferred triols are trimethylolpropane, trimethylolethane, glycerol,
diglycerol and
triglycerol, and polyetherols thereof based on ethylene oxide and/or propylene
oxide.
Also suitable are furthermore 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.
Also suitable are 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 mixtures of such reaction products.
It is also possible to use mixtures of at least trifunctional polyalcohols.
For example,
one to six, preferably one to four, particularly preferably one to three, very
particularly
preferably one to two and in particular one at least trifunctional alcohol can
be used.
,,as originally filed"
CA 02879574 2015-01-20
PF73489
7
In this connection, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-
butanediol,
1,5-pentanediol, 1,6-hexanediol, and diethylene glycol, triethylene glycol,
dipropylene
glycol, tripropylene glycol, polyethylene glycol with an average molecular
weight
between 200 and 1000 g/mol, glycerol, diglycerol, triglycerol,
trimethylolpropane,
trimethylolethane, di(trimethylolpropane), 1,2,4-butanetriol, 1,2,6-
hexanetriol,
pentaerythritol, sucrose, sorbitol or glucaric acid, and polyetherols thereof
based on
ethylene oxide and/or propylene oxide, or a mixture thereof are preferred as
component B.
Particular preference is given to diethylene glycol or polyethylene glycol
with an
average molecular weight between 200 and 1000 g/mol, trimethylolpropane,
glycerol or
diglycerol, triglycerol, and polyetherols thereof based on ethylene oxide
and/or
propylene oxide, or a mixture thereof.
Component C
In addition to the citric acid, further carboxylic acids, in particular
saturated dicarboxylic
acids, can be condensed in, in which case the fraction of further
polycarboxylic acids
should be at most 30 molc1/0 compared with the amount of citric acid used.
Preferably,
the polycarboxylic acids of component C comprise no sulfonate groups.
Suitable saturated dicarboxylic acids are, for example, aliphatic dicarboxylic
acids,
such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
pimelic acid,
suberic acid, azeleic 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.
The specified saturated dicarboxylic acids can also be substituted with one or
more
radicals selected from
C1-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,
as originally filed"
CA 02879574 2015-01-20
PF73489
,
' 8
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 is 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.
Exemplary 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 and
octadecenylsuccinic acid.
The dicarboxylic acids can either be used as they are or in the form of
derivatives.
Derivatives are preferably understood as meaning the relevant anhydrides in
monomeric or else 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, as well as mixed esters, preferably
mixed esters
with different C1-C4-alkyl components, particularly preferably mixed methyl
ethyl esters.
Among these, preference is given to the anhydrides and the mono- or dialkyl
esters,
particularly preferably the anhydrides and the mono- or di-C1-C4-alkyl esters
and very
particularly preferably the anhydrides.
Within the context of this specification, C1-C4-alkyl means methyl, ethyl,
isopropyl,
n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl,
ethyl and n-butyl,
particularly preferably methyl and ethyl and very particularly preferably
methyl.
,,as originally filed"
PF73489 CA 02879574 2015-01-20
9
,
Particularly preferably, malonic acid, succinic acid, glutaric acid, adipic
acid, sebacic
acid, octadecenylsuccinic anhydride, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic
acids
(hexahydrophthalic acids as cis or trans compounds or mixtures thereof) are
used.
Further preferred dicarboxylic acids are glucaric acid and tartaric acid.
The amount of dicarboxylic acid is not more than 30 mol% compared with the
amount
of citric acid used, preferably not more than 20%, very particularly
preferably not more
than 15%.
Component D
Suitable components D are alkyl- or alkenylcarboxylic acids, such as, for
example,
long-chain, linear or branched carboxylic acids having 6 to 30 carbon atoms,
preferably
8 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the alkyl or
alkenyl
radical, such as octanoic acid, nonanoic acid, decanoic acid, undecanoic acid,
dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid,
arachic acid,
behenic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid,
linolenic acid,
arachidonic acid or Li, Na, K, Cs, Ca or ammonium salts thereof.
It is also possible to use mixtures.
Preferably, oleic acid, palmitic acid, linoleic acid, stearic acid, lauric
acid and ricinoleic
acid are used.
The alkyl- or alkenylcarboxylic acids can also be used in the form of their
carboxylic
acid alkyl esters. Preference is given to using the methyl esters.
Suitable long-chain alcohols are, for example, linear or branched alcohols
having 6 to
carbon atoms, preferably 8 to 22 carbon atoms, in particular 10 to 18 carbon
atoms
in the linear or branched alkyl radical, such as octan-1-ol, decan-1-ol,
lauryl alcohol,
30 myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, behenyl
alcohol,
9-hexadecen-1-ol and 9-octadecen-1-ol.
Preference is given to using lauryl alcohol and stearyl alcohol.
Exemplary representatives of alkyl- or alkenylamines which may be mentioned
are:
linear or branched alkylamines having 6 to 30 carbon atoms, preferably 8 to 22
carbon
atoms, in particular 10 to 18 carbon atoms, in the linear or branched alkyl
radical, such
,,as originally filed"
P F73489 CA 02879574 2015-01-20
as hexylamine, octylamine, nonylamine, decylamine, dodecylamine,
tetradecylamine,
hexadecylamine, octadecylamine and mixtures thereof.
Suitable long-chain isocyanates are linear or branched isocyanates having 6 to
30
5 carbon atoms, preferably 8 to 22 carbon atoms, in particular 10 to 18
carbon atoms, in
the linear or branched alkyl radical, such as octyl isocyanate, dodecyl
isocyanate,
stearic isocyanate and mixtures thereof.
The molar ratio of (component A + component B) to component D is preferably
10:0.1
10 to 0.5:0.1, particularly preferably 5:0.1 to 1:0.1.
The present invention further provides hydrophobicized branched polyesters as
described above and the process for the preparation thereof.
Preparation process
The process for preparing the branched polyesters based on citric acid can be
carried
out without dilution or in the presence of an organic 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-xylane, xylene as isomer mixture, ethylbenzene,
chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, suitable
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.
The amount of added solvent is at least 0.1% by weight, based on the mass of
the
starting materials used and 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 starting materials used and to be reacted, for
example
1.01-to 10-fold.
Preferably, the reaction is carried out without addition of solvent.
To carry out the process, it is possible to work in the presence of a water-
withdrawing
agent as additive, which is added at the start of the reaction. Of suitability
are, for
example, molecular sieves, in particular 4A molecular sieve, MgSO4 and Na2SO4.
,,as originally filed"
PF73489 CA 02879574 2015-01-20
,
11
During the reaction, it is also possible to add further water-withdrawing
agent or to
replace water-withdrawing agent with fresh water-withdrawing agent. During the
reaction, it is also possible to distill off water and/or alcohol that is
formed and, for
example, to use a water separator, in which the water is removed with the help
of an
entrainer.
Preferably, the process is carried out in the absence of catalysts.
However, it is also possible to carry out the process in the presence of at
least one
catalyst. As preferred catalysts may 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 considered to
be Lewis
acids, i.e. those compounds according to Rompps Chemie-Lexikon, under "Saure-
Base-Begrifr [Acids and Bases], which can accept an electron pair into the
valence
shell of one of their atoms.
Acidic inorganic catalysts to be mentioned are, for example, sulfuric acid,
sulfates and
hydrogensulfates, such as sodium hydrogensulfate, phosphoric acid, phosphonic
acid,
hydrophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH 5
6, in
particular 5 5) and acidic aluminum oxide. Furthermore, it is 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
may in
each case be identical or different and, independently of one another, are
selected
from C1-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
is 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.
Preference is given to using titanium(IV) tetrabutoxide.
,,as originally filed"
P F73489 CA 02879574 2015-01-20
12
Preferred acidic organometallic catalysts are selected for example from
dialkyltin
oxides (R1)2SnO or dialkyltin diesters (R1)2Sn(0R2)2, where R' is as defined
above and
can be identical or different.
R2 can have the same meanings as R1 and 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.
Examples are 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, dibutyltin dimaleate or dioctyltin diacetate.
Organoantimony, organobismuth or organoaluminum catalysts are also
conceivable.
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 sulfonic acid-group-containing polystyrene resins which
have
been crosslinked with about 2 mol /0 of divinylbenzene.
Combinations of two or more of the aforementioned catalysts can also be used.
It is
also possible 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 by weight of catalyst, particularly
preferably
2 to 5000 ppm by weight, based on the total mass of the hydroxyl group- and
the
carboxyl group-containing compounds.
If it is desired to use acidic inorganic, organometallic or organic catalysts,
then the
process is carried out at temperatures from 60 to 140 C. Preference is given
to working
at temperatures of from 80 to 140, particularly preferably at 100 to 130 C.
õas originally filed"
P F73489 CA 02879574 2015-01-20
13
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 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 catalyst, then the process is carried out
at
temperatures from 20 and up to 120 C, preferably 20 to 100 C and particularly
preferably not more than 20-80 C.
The process 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 gases, among which argon in particular is to be
mentioned.
The process is carried out at temperatures of from 60 to 140 C. Preference is
given to
working at temperatures of from 80 to 140, particularly preferably at 100 to
130 C.
The pressure conditions of the process are generally not critical. It is
possible to work
at significantly reduced pressure, for example at 10 to 500 mbar. The process
can also
be carried out at pressures above 500 mbar. For reasons of simplicity, the
reaction is
preferably at atmospheric pressure; however, an implementation at slightly
elevated
pressure, for example up to 1200 mbar, is also possible. It is also possible
to work
under significantly increased pressure, for example at pressures up to 10 bar.
Preferably, the reaction is at reduced pressure or atmospheric pressure,
particularly
preferably at atmospheric pressure.
õas originally filed"
PF73489 CA 02879574 2015-01-20
14
The reaction time of the process is usually 10 minutes to 5 days, preferably
30 minutes
to 48 hours and particularly preferably 1 to 12 hours.
When the reaction 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 decolorization, 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, 0.1-50% by weight, preferably 0.5 to 25% by weight,
particularly
preferably 1-10% 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 decolorizing agent
to the
reaction mixture and subsequent filtration, or by passing the reaction mixture
over a
bed of a decolorizing agent in the form of any desired suitable shaped bodies.
The decolorization 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
optional prewashing, neutralization, washing or solvent removal.
The reaction mixture can furthermore 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 means of 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 process, 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
,,as originally filed"
P F73489 CA 02879574 2015-01-20
single-stage or multi-stage, preferably single-stage, extractions, and also
those in
cocurrent or countercurrent mode, preferably countercurrent mode.
However, in one preferred embodiment, it is possible to dispense with a
washing,
5 neutralization and decolorization.
The branched polyesters have molecular weights M5 of from 400 to 5000 g/mol,
preferably 400 to 3000 g/mol, particularly preferably from 500 to 2500 g/mol,
and
molecular weights Mw of from 500 to 50 000 g/mol, preferably 700 to 25 000
g/mol,
10 particularly preferably 700 to 15 000.
The molecular weights of the branched polyesters were determined by gel
permeation
chromatography (GPC) (eluent: THF; standard: PMMA, detector: refractive index
detector).
The branched polyesters have acid numbers of from 60 to 600 mg KOH/g of
polymer,
preferably 80 to 500 mg KOH/g of polymer and very particularly preferably 100
to
450 mg KOH/g of polymer. The acid numbers were determined in accordance with
DIN 53402.
The branched polyesters 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) at a heating rate of 20 K/min.
Cleaner formulations
A further embodiment of the invention is given by mixtures of the branched
polyesters
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, washing compositions 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 processes known to the person skilled in the art. In this connection, solid
formulations such as powders, tablets and liquid formulations are to be
mentioned.
,,as originally filed"
P F73489 CA 02879574 2015-01-20
16
The invention therefore further provides the use of the branched polyesters
according
to the invention, or mixtures thereof, in washing compositions, cleaners or
detergents,
in particular in dishwashing compositions.
They can be used particularly advantageously in machine dishwashing
compositions.
They are characterized here in particular by their deposit-inhibiting effect
both towards
inorganic and 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 soil 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 one or more phases, as tablets or in the form of other
dosage units,
packaged or unpackaged.
The branched polyesters can be used either in multicomponent product systems
(separate use of detergent, rinse aid and regenerating salt) or in those
dishwashing
compositions in which the functions of detergent, rinse aid and regenerating
salt are
combined in one product (3-in-1 products, 6-in-1 products, 9-in-1 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, bleach catalysts, alkali carriers, polymeric
dispersants,
corrosion inhibitors, antifoams, dyes, fragrances, fillers, tablet
disintegrants, organic
solvents, tableting auxiliaries, disintegrants, thickeners, solubility
promoters and water,
,,as originally filed"
P F73489 CA 02879574 2015-01-20
17
where the sum of components a) to h) is 100% by weight.
As component b), the cleaning formulations according to the invention can
comprise
one or more complexing agents. Preferred complexing agents are selected from
the
group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid
and
methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid,
hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid
diacetic
acid, and salts thereof. Particularly preferred complexing agents b) are
methylglycinediacetic acid and salts thereof.
As component c), the cleaner according to the invention can comprise
phosphates. If
the cleaner comprises phosphates, it generally comprises these in amounts of
from 1
to 70% by weight, preferably from 5 to 60% by weight, particularly preferably
from 20 to
55% by weight.
Among the large number of commercially available phosphates, the alkali metal
phosphates, particularly preferably pentasodium or pentapotassium triphosphate
(sodium or potassium tripolyphosphate), are of the greatest importance in the
detergents and cleaners industry.
Of suitability as phosphates for dishwashing compositions are in particular
alkali metal
phosphates and polymeric alkali metal phosphates, which may be present in the
form
of their alkaline, neutral or acidic sodium or potassium salts. Examples of
phosphates
of this type are trisodium phosphate, tetrasodium diphosphate, disodium
dihydrogen-
diphosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate,
oligomeric trisodium phosphate with a degree of oligomerization of from 5 to
1000,
preferably 5 to 50, and the corresponding potassium salts, or mixtures of
sodium
hexametaphosphate and the corresponding potassium salts, or mixtures of the
sodium
and potassium salts. Tripolyphosphate salts are particularly preferred. These
are used
in amounts of from 30 to 65% by weight, preferably 35 to 60% by weight,
expressed as
water-free active substance and based on the total cleaning formulation.
As component d), the cleaner according to the invention can comprise builders
and
cobuilders. Builders and cobuilders are water-soluble or water-insoluble
substances
whose main task consists in the binding of calcium and magnesium ions.
,,as originally filed"
PF73489 CA 02879574 2015-01-20
18
These may be low molecular weight carboxylic acids and salts thereof such as
alkali
metal citrates, in particular anhydrous trisodium citrate or trisodium citrate
dihydrate,
alkali metal succinates, alkali metal malonates, fatty acid sulfonates,
oxydisuccinate,
alkyl- or alkenyldisuccinates, gluconic acids, oxadiacetates,
carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate,
tartrate
monoacetate, tartrate diacetate and a-hydroxypropionic acid.
A further substance class with cobuilder properties which may be present in
the
cleaners according to the invention is that of the phosphonates. These are in
particular
hydroxyalkane- and aminoalkanephosphonates. Among the
hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of
particular importance as cobuilder. It is preferably used as sodium salt, the
disodium
salt being neutral and the tetrasodium salt alkaline (pH 9). Suitable
aminoalkanephosphonates are preferably
ethylenediaminetetramethylenephosphonate
(EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and higher
homologs thereof. They are preferably used in the form of the neutral sodium
salts, e.g.
as hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP. As
builder,
preferably HEDP is used here from the class of phosphonates. The
aminoalkanephosphonates moreover have a pronounced heavy metal binding
capacity. Accordingly, especially if the compositions also comprise bleaches,
it may be
preferred to use aminoalkanephosphonates, in particular DTPMP, or to use
mixtures of
the specified phosphonates.
A further substance class in the builder system is that of the silicates.
Crystalline sheet
silicates with the general formula NaMSi902x+1 yH20 may be present, where M is
sodium or hydrogen, xis a number from 1.9 to 22, preferably from 1.9 to 4,
where
particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to
33,
preferably 0 to 20. In addition, amorphous sodium silicates with an Si02:Na20
ratio of 1
to 3.5, preferably from 1.6 to 3 and in particular from 2 to 2.8, can be used.
Furthermore, carbonates and hydrogencarbonates are used, of which the alkali
metal
salts, in particular sodium salts, are preferred. Preferred amounts are 5 to
50% by
weight, particularly preferably 10 to 40% by weight and in particular 15 to
30% by
weight.
,,as originally filed"
P F73489 CA 02879574 2015-01-20
19
As component e), the cleaning formulations according to the invention comprise
weakly
foaming or low-foam nonionic surfactants. These are generally present in
fractions of
from 0.1 to 20% by weight, preferably from 0.1 to 15% by weight, particularly
preferably
from 0.25 to 10% by weight.
Suitable nonionic surfactants comprise the surfactants of the general formula
(Ill)
R18-0-(CH2CH20)p-(CHR17CH20)m-R19 (Ill)
in which R18 is a linear or branched alkyl radical having 8 to 22 carbon
atoms,
R17 and R19, independently of one another, are hydrogen or a linear or
branched alkyl
radical having 1-10 carbon atoms or H, where R17 is preferably methyl,
p and m, independently of one another, are 0 to 300. Preferably, p = 1-100 and
m = 0-30.
The surfactants of the formula (Ill) may either be random copolymers or block
copolymers, preference being given to block copolymers.
Furthermore, di- and multiblock copolymers, formed from ethylene oxide and
propylene
oxide, can be used, which are commercially available for example under the
name
Pluronic (BASF SE) or Tetronic (BASF Corporation). Furthermore, reaction
products
of sorbitan esters with ethylene oxide and/or propylene oxide can be used.
Likewise of
suitability of amine oxides or alkyl glycosides. An overview of suitable
nonionic
surfactants is given in EP-A 851 023 and DE-A 198 19 187.
Mixtures of two or more different nonionic surfactants may also be present.
The formulations can also comprise anionic or zwitterionic surfactants,
preferably in a
mixture with nonionic surfactants. Suitable anionic and zwitterionic
surfactants are
likewise specified in EP-A 851 023 and DE-A 198 19 187.
As component f), the cleaning formulations according to the invention can
comprise
bleaches and optionally bleach activators.
Bleaches are subdivided into oxygen bleaches and chlorine-containing bleaches.
Alkali
metal perborates and hydrates thereof, and also alkali metal percarbonates,
are used
õas originally filed"
P F73489 CA 02879574 2015-01-20
as oxygen bleaches. Preferred bleaches here are sodium perborate in the form
of the
mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium
percarbonate.
Persulfates and hydrogen peroxide can likewise be used as oxygen bleaches.
5
Typical oxygen bleaches are also organic peracids, such as, for example,
perbenzoic
acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid,
phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-
diperoxyazeleic
acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-dioic acid.
Moreover, the following oxygen bleaches may also be used in the cleaner
formulation:
Cationic peroxy acids which are described in the patent applications US
5,422,028,
US 5,294,362 and US 5,292,447, and sulfonyl peroxy acids which are described
in the
patent application US 5,039,447.
Oxygen bleaches are used in amounts of in general 0.5 to 30% by weight,
preferably
from 1 to 20% by weight, particularly preferably from 3 to 15 % by weight,
based on the
total cleaner formulation.
Chlorine-containing bleaches and the combination of chlorine-containing
bleaches with
peroxide-containing bleaches can likewise be used. Known chlorine-containing
bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-
chlorosulfamide,
chloramine T, dichloramine T, chloramine B, N,N'-dichlorobenzoylurea,
p-toluenesulfonedichloroamide or trichloroethylamine. Preferred chlorine-
containing
bleaches are sodium hypochlorite, calcium hypochlorite, potassium
hypochlorite,
magnesium hypochlorite, potassium dichloroisocyanurate or sodium
dichloroisocyanurate.
Chlorine-containing bleaches are used in amounts of in general 0.1 to 20% by
weight,
preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8%
by weight,
based on the total cleaner formulation.
Furthermore, bleach stabilizers such as, for example, phosphonates, borates,
metaborates, metasilicates or magnesium salts can be added in small amounts.
,,as originally filed"
PF73489 CA 02879574 2015-01-20
21
Bleach activators 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 substituted perbenzoic acid. Compounds which
comprise
one or more N- or 0-acyl groups and/or optionally substituted benzoyl groups,
for
example substances from the class of anhydrides, esters, imides, acylated
imidazoles
or oximes, are suitable. Examples are tetraacetylethylenediamine (TAED),
tetraacetylmethylenediamine (TAM D), tetraacetylglycoluril (TAGU),
tetraacetylhexylenediamine (TAHD), N-acylimides, such as, for example,
N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, such as, for example,
n-nonanoyl- or isononanoyloxybenzenesulfonates (n- or iso-NOBS),
pentaacetylglucose (FAG), 1,5-diacety1-2,2-dioxohexahydro-1,3,5-triazine
(DADHT) or
isatoic anhydride (ISA). Likewise suitable as bleach activators are nitrile
quats such as,
for example, N-methylmorpholinioacetonitrile salts (MMA salts) or
trimethylammonioacetonitrile salts (TMAQ salts).
Preferably, bleach activators from the group consisting of polyacylated
alkylenediamines, particularly preferably TAED, N-acylimides, particularly
preferably
NOSI, acylated phenolsulfonates, particularly preferably n- or iso-NOBS, MMA
and
TMAQ are suitable.
Bleach activators are used in amounts of in general 0.1 to 10% by weight,
preferably
from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight,
based on the
total cleaner formulation.
In addition to the conventional bleach activators, or instead of them, so-
called bleach
catalysts can also be incorporated into the rinse-aid particles. These
substances are
bleach-boosting transition metal salts or transition metal complexes such as,
for
example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes
or
-carbonyl complexes. It is also possible to use manganese, iron, cobalt,
ruthenium,
molybdenum, titanium, vanadium and copper complexes with nitrogen-containing
tripod
ligands, as well as cobalt-, iron-, copper- and ruthenium-amine complexes as
bleach
catalysts.
As component g), the cleaning formulations according to the invention can
comprise
enzymes. Between 0 and 8% by weight of enzymes, based on the total
preparation,
can be added to the cleaner in order to increase the performance of the
cleaner or to
as originally filed"
P F73489 CA 02879574 2015-01-20
,.
22
,
ensure the same quality of cleaning performance under milder conditions. The
enzymes used most often include lipases, amylases, cellulases and proteases.
Furthermore, esterases, pectinases, lactases and peroxidases, for example, can
also
be used.
The cleaners according to the invention can moreover comprise, as component
i),
further additives such as anionic or zwitterionic surfactants, bleach
catalysts, alkali
carriers, corrosion inhibitors, antifoams, dyes, fragrances, fillers, tablet
disintegrants,
organic solvents and water.
Furthermore, the cleaners according to the invention can comprise 0 to 50% by
weight
of one or more further additives such as alkali carriers, corrosion
inhibitors, antifoams,
dyes, fragrances, fillers, organic solvents, tableting auxiliaries,
disintegrants, solubility
promoters and water.
As further constituents of the cleaner formulation, alkali carriers may be
present.
Besides the ammonium or alkali metal carbonates, ammonium or alkali metal
hydrogen-carbonates and ammonium or alkali metal sesquicarbonates already
specified among the builder substances, it is also possible to use ammonium or
alkali
metal hydroxides, ammonium or alkali metal silicates and ammonium or alkali
metal
metasilicates, and mixtures of the aforementioned substances, as alkali
carriers.
As corrosion inhibitors, silver anticorrosives from the group of triazoles,
benzotriazoles,
bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal
salts or
complexes can be used.
To prevent glass corrosion, which is evident from clouding, iridescence,
streaking and
lines on the glasses, glass corrosion inhibitors are used. Preferred glass
corrosion
inhibitors are from the group of magnesium, zinc and bismuth salts and
complexes.
Paraffin oils and silicone oils can optionally be used as antifoams and for
protecting
plastic and metal surfaces. Antifoams are generally used in fractions of from
0.001% by
weight to 5% by weight. Moreover, dyes such as, for example, patent blue,
preservatives such as, for example, Kathon CG, perfumes and other fragrances
can be
added to the cleaning formulation according to the invention.
,,as originally filed"
PF73489 CA 02879574 2015-01-20
23 =
A suitable filler is, for example, sodium sulfate.
The invention further provides the use of the branched polyesters according to
the
invention and mixtures thereof as scale inhibitors in water-conveying systems.
Water-conveying systems in which the polymers according to the invention can
be
used are processes for water treatment, in particular seawater and brackish
water
desalination plants, cooling water systems and boiler feed water systems and
industrial
process waters. The desalination plants can be thermal in nature or be based
on
membrane processes such as reverse osmosis or electrodialysis.
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 dosage is
governed by
the requirements of the particular application and/or by the operating
conditions of the
respective process. For example, the polymers are preferably used in
concentrations of
from 0.5 mg/I to 10 mg/I in the case of thermal seawater desalination. In
industrial
cooling circuits or boiler feed water systems, polymer concentrations up to
100 mg/I are
used. Often, water analyses are carried out in order to ascertain the fraction
of scale-
forming salts and thus the optimum dosage.
It is also possible to add to the water-conveying systems formulations which,
besides
the polymers according to the invention, can comprise according to
requirements,
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. 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 present invention provides branched polyesters which can be used for
cleaning
purposes and for the purpose of water treatment and are nevertheless
biodegradable.
These polymeric effect substances, which have a low toxicity, can be prepared
by
means of a technically relatively simple and cost-effective process and can be
readily
incorporated into formulations for cleaning purposes in their various
presentation forms.
as originally filed"
P F73489 CA 02879574 2015-01-20
24
The invention is further illustrated by the examples, without the examples
limiting the
subject matter of the invention.
Examples
Preparation of the polyesters according to the invention
General remarks:
The molecular weights were determined by gel permeation chromatography (GPO)
(eluent: THF; standard: PMMA; detector: refractive index detector).
The acid numbers (mg KOH/g of polymer) were determined in accordance with
DIN 53402.
TMP is understood as meaning trimethylolpropane.
TMP x n EO is understood as meaning trimethylolpropane alkoxylated with n mol
of
ethylene oxide, where n can be an average value (number-average).
PEG 200 is understood as meaning a polyethylene glycol with an average
molecular
weight of 200 g/mol.
Polyglycerol 3 is understood as meaning triglycerol.
Polymer 1: Polycondensate of citric acid monohydrate/TMP 1.5:1.0
A 500 ml round-bottomed flask equipped with stirrer, internal thermometer, gas
inlet
tube and descending condenser with collecting vessel was charged with 210.4 g
(1.00 mol) of citric acid monohydrate and 89.6 g (0.67 mol) of TMP, and 0.1 g
(400 ppm) of titanium(IV) tetrabutoxide. Under nitrogen gassing, the mixture
was
heated to 130 C and held at this temperature for 2 h with stirring, during
which water of
reaction and water of crystallization that was liberated was separated off via
the
descending condenser. The reaction was then ended 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 = 345 mg KOH/g of polymer
Mr, = 570 g/mol, M, = 2580 g/mol
Polymer 2: Polycondensate of citric acid monohydrate/TMP 2.0:1.0
,,as originally filed"
P F73489 CA 02879574 2015-01-20
A 500 ml round-bottomed flask equipped with stirrer, internal thermometer, gas
inlet
tube and descending condenser with collecting vessel was charged with 151.6 g
(0.77 mol) of citric acid monohydrate and 48.8 g (0.37 mol) of TMP, and 0.06 g
(300 ppm) of titanium(IV) tetrabutoxide. Under nitrogen gassing, the mixture
was
5 heated to 130 C and held at this temperature for 2 h with stirring,
during which water of
reaction and water of crystallization that was liberated was separated off via
the
descending condenser. The reaction was then ended by cooling to room
temperature.
The product was obtained in the form of a yellow water-soluble resin.
The following characteristic data were determined:
10 Acid number = 398 mg KOH/g of polymer
M, = 550 g/mol, Mw = 3990 g/mol
Polymer 3: Polycondensate of citric acid monohydrate/TMP/TMPx12.2 EO
1.7:0.5:0.5
15 A 500 ml round-bottomed flask equipped with stirrer, internal
thermometer, gas inlet
tube and descending condenser with collecting vessel was charged with 141.1 g
(0.67 mol) of citric acid monohydrate, 132.4 g (0.20 mol) of TMP x 12 EO and
26.5 g
(0.20 mol) of TMP, and 0.1 g (400 ppm) of titanium(IV) tetrabutoxide. Under
nitrogen
gassing, the mixture was heated to 130 C and held at this temperature for 2.5
h with
20 stirring, during which water of reaction and water of crystallization
that was liberated
was separated off via the descending condenser. The reaction was then ended by
cooling to room temperature.
The product was obtained in the form of a yellow water-soluble resin.
The following characteristic data were determined:
25 Acid number = 262 mg of KOH/g of polymer
Mn = 1170 g/mol, Mw = 2260 g/mol
Polymer 4: Polycondensate of citric acid monohydrate/polyglycerol 3 ¨ 3.0:1.0
A 500 ml round-bottomed flask equipped with stirrer, internal thermometer, gas
inlet
tube and descending condenser with collecting vessel was charged with 217.4 g
(1.03 mol) of citric acid monohydrate and 82.4 g (0.34 mol) of polyglycerol 3,
and
0.015 g (50 ppm) of sulfuric acid. Under nitrogen gassing, the mixture was
heated to
130 C and held at this temperature for 4 h with stirring, during which water
of reaction
and water of crystallization that was liberated was separated off via the
descending
condenser. The reaction was then ended by cooling to room temperature.
õas originally filed"
PF73489 CA 02879574 2015-01-20
26
The product was obtained in the form of a yellow water-soluble resin.
The following characteristic data were determined:
Acid number = 428 mg of KOH/g of polymer
Mn = 1320 g/mol, M, = 1600 g/mol
Polymer 5: Polycondensate of citric acid monohydrate/polyglycerol 3/TMP
4.0:1.0:1.0
A 500 ml round-bottomed flask equipped with stirrer, internal thermometer, gas
inlet
tube and descending condenser with collecting vessel was charged with 207.5 g
(1.00 mol) of citric acid monohydrate, 59.3 g (0.25 mol) of polyglycerol 3 and
33.1
(0.25 mol) of TMP, and 0.1 g (400 ppm) of titanium(IV) tetrabutoxide. Under
nitrogen
gassing, the mixture was heated to 130 C and held at this temperature for 3.5
h with
stirring, during which water of reaction and water of crystallization that was
liberated
was separated off via the descending condenser. The reaction was then ended 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 = 378 mg of KOH/g of polymer
= 520 g/mol, Mw = 700 g/mol
Polymer 6: Polycondensate of citric acid monohydrate/diethylene glycol/TMP
1.7:0.5:0.5 (without cat.)
A 500 ml round-bottomed flask equipped with stirrer, internal thermometer, gas
inlet
tube and descending condenser with collecting vessel was charged with 224.5 g
(1.07 mol) of citric acid monohydrate, 33.3 g (0.31 mol) of diethylene glycol
and 42.2 g
(0.31 mol) of TMP. Under nitrogen gassing, the mixture was heated to 130 C and
held
at this temperature for 2.0 h with stirring, during which water of reaction
and water of
crystallization that was liberated was separated off via the descending
condenser. The
reaction was then ended by cooling to room temperature.
The product was obtained in the form of a dark yellow water-soluble resin. The
following characteristic data were determined:
Acid number = 412 mg of KOH/g of polymer
= 1300 g/mol, M= 3500 g/mol
as originally filed"
PF73489 CA 02879574 2015-01-20
27
Polymer 7: Polycondensate of citric acid monohydrate/TMP/PEG 200 1.7:0.5:0.5
(without cat.)
A 1000 ml round-bottomed flask equipped with stirrer, internal thermometer,
gas inlet
tube and descending condenser with collecting vessel was charged with 204.4 g
(0.97 mol) of citric acid monohydrate, 57.2 g (0.29 mol) of PEG 200 and 38.4 g
(0.29 mol) of TMP. Under nitrogen gassing, the mixture was heated to 130 C and
held
at this temperature for 8 h with stirring, during which water of reaction and
water of
crystallization that was liberated was separated off via the descending
condenser. The
reaction was then ended 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 = 347 mg of KOH/g of polymer
Mr, = 890 g/mol, M, = 2700 g/mol
Polymer 8: Polycondensate of citric acid monohydrate/TMP/oleic acid
1.5:1.0:0.2
(without cat.)
A 1000 ml round-bottomed flask equipped with stirrer, internal thermometer,
gas inlet
tube and descending condenser with collecting vessel was charged with 186.9 g
(0.88 mol) of citric acid monohydrate, 79.6 g (0.593 mol) of
trimethylolpropane and
33.5 g of oleic acid (0.119 mol). Under nitrogen gassing, the mixture was
heated to
130 C and held at this temperature for 2 h with stirring, during which water
of reaction
and water of crystallization that was liberated was separated off via the
descending
condenser. The reaction was then ended 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 = 321 mg of KOH/g of polymer
Mn = 1400 g/mol, M = 2800 g/mol
Polymer 9: Polycondensate of citric acid monohydrate/IMP/oleic acid
1.5:0.5:0.1
(without cat.)
A 1000 ml round-bottomed flask equipped with stirrer, internal thermometer,
gas inlet
tube and descending condenser with collecting vessel was charged with 186.9 g
(0.88 mol) of citric acid monohydrate, 79.6 g (0.593 mol) of
trimethylolpropane and
as originally filed"
PF73489 CA 02879574 2015-01-20
28
16.75 g of oleic acid (0.06 mol). Under nitrogen gassing, the mixture was
heated to
130 C and held at this temperature for 2 h with stirring, during which water
of reaction
and water of crystallization that was liberated was separated off via the
descending
condenser. The reaction was then ended 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 = 314 mg of KOH/g of polymer
Mn = 1700 g/mol, M = 3000 g/mol
Calcium carbonate inhibition test
A solution of NaHCO3, Mg2SO4, CaCl2 and polymer is shaken in a waterbath for 2
h at
70 C. After filtering the still-warm solution through a 0.45 pm Milex filter,
the Ca content
of the filtrate is ascertained by complexometry or by means of a Ca2+-
selective
electrode, and the CaCO3 inhibition is ascertained in % by means of a
before/after
comparison (see formula l).
Ca2+ 215 mg/L
Mg2+ 43 mg/L
HCO3- 1220 mg/L
Na + 460 mg/L
Cl- 380 mg/L
S042- 170 mg/L
Polymer 5 mg/L
Temperature 70 C
Time 2 hours
pH 8.0-8.5
CaCO3 inhibition ( /0) = mg of (Ca2+) after 24 h - mg of (Ca2+) blank value
after 24 h
*100
mg of (Ca2+) zero value - mg of (Ca2+) blank value after 24 h
as originally filed"
PF73489 CA 02879574 2015-01-20
29
Table 1
Inhibition [ /0]
Example
1 40.9
2 48.5
3 55.4
4 32.1
36.7
6 28.2
7 34.1
8 44.1
9 30.5
5 The polymers were tested in the following phosphate-free formulations PF1
and PF2,
and also in the phosphate-based formulation P1. Table 2
PF 1 PF 2 P1
Protease 2.5 2.5 1
Amylase 1.0 1.0 0.2
Nonionic surfactant 5.0 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 19.5 19.5 18.8
Sodium citrate dihydrate 35
Methylglycinediacetic acid 10 45
Hydroxyethane-(1,1- 0.5 0.5 0.5
diphosphonic acid)
Data in A by weight based on the total amount of all components
as originally filed"
P F73489 CA 02879574 2015-01-20
The following experimental conditions were observed:
Dishwasher: Miele G 1222 SCL
Program: 65 C (with prewash)
Dishes: 3 knives (WMF Tafelmesser Berlin, monobloc)
5 3 Amsterdam 0.2L drinking glasses
3 "OCEAN BLAU" breakfast plates (MELAMINE)
3 porcelain plates: 19 cm plates with rims flat
Arrangement: Knives in the cutlery drawer, glasses in the upper baskets,
plates in
the lower basket
10 Dishwashing detergent: 18 g
Addition of soil: 50 g of ballast soil is added in thawed form with the
formulation after
the prewash; for composition see below
Rinse temperature: 65 C
Water hardness: 21 German hardness (Ca/Mg):HCO3 (3:1):1.35
15 Wash cycles: 6; break in between for 1 h in each case (10 min
with door open, 50
min with door closed)
Evaluation: Visually after 6 wash cycles
The evaluation of the dishes was carried out after 6 cycles in a darkened
chamber
20 under light behind an aperture diaphragm using a grading scale from 10
(very good) to
1 (very poor). Grades from 1-10 for spotting (very many, intensive spots = 1
ranging to
no spots = 10) and also for filming (1 = very severe filming, 10 = no filming)
were
awarded.
Composition of the ballast soil:
25 Starch: 0.5% potato starch, 2.5% gravy
Fat: 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
30 Result:
The formulation containing polymer are characterized in particular by their
very high
film-inhibiting effect towards inorganic and organic deposits on glass,
knives, porcelain
and plastic components. Furthermore, they increase the cleaning power of the
dishwashing detergent and encourage the water to run off from the dishes.
õas originally filed"
P F73489 CA 02879574 2015-01-20
31
The tables below list the summed grades for film formation and spotting on
knives and
drinking glasses.
Phosphate-free formulation PF 1
Polymer Knives (F + S) Glasses (F + S)
2 17 13
3 18 11
5 18 11
8 16 12
without 8 7
Phosphate-free formulation PF 2
Polymer Knives (F + S) Glasses (F + S)
2 14 12
3 11 10
5 14 11
8 13 13
without 7 8
õas originally filed"
