1. An additive for hydraulic compositions, comprising a mixture of the compounds of the following formulas (I), (II) and (III): in which: the groups (CH2-CH2-O) and (CH2-CH(CH3)-O) are arranged in blocks, alternately or randomly, n, n1 and n2, independently of one another, are integers which vary between 1 and 150 (inclusive), m, m1 and m2, independently of one another, are integers which vary between 0 and 150 (inclusive), with n + m ≥ 10, with n1 + m1 ≥ 1, with n2 + m2 ≥ 1, the group R is chosen from one or more of the elements H, CH3, C2H5, C3H7, C4H9, PO3X2 or the group NYZ in which: Y and Z may be identical or different, Y represents (EO)n3 – (PO)m3 – PO3X2 or (EO)n3 – (PO)m3 – H, Z represents (EO)n4 – (PO)m4 – PO3X2 or (EO)n4 – (PO)m4 – H, 29 n3 and n4, independently of one another, are integers which vary between 1 and 150 (inclusive) and m3 and m4, independently of one another, are integers which vary between 0 and 150 (inclusive), X represents H or M and M represents a monovalent, divalent or trivalent cation.

2. Additive according to claim 1, in which n1 + m1 ≤ 10 and n2 + m2 ≤ 10.

3. Additive according to any one of the preceding claims, according to which, in formulas (I), (II) and (III), n1 and n2 are equal to 1 and m1 and m2 are equal to 0.

4. Additive according to any one of the preceding claims, according to which, in formulas (I), (II) and (III), R represents CH3.

5. Additive according to any one of the preceding claims, according to which M is chosen from the group consisting of the potassium ion, sodium ion, lithium ion, calcium ion, magnesium ion, ammonium ion and a mixture of these ions.

6. Additive according to any one of the preceding claims, according to which, in formula (I), m is equal to 0.

7. Additive according to any one of the preceding claims, according to which in formula (I), n varies between 20 and 120 (inclusive).

8. A hydraulic composition comprising: - water, - a hydraulic binder comprising a cement and - at least one additive for hydraulic compositions according to any one of the claims 1 to 7.

9. Hydraulic composition according to claim 8, comprising, relative to the total weight of the composition: 30 - from 2 to 15% by weight of water, - from 10 to 30% by weight of hydraulic binder comprising a cement and - from 0.05 to 3% by weight of said at least one additive.

10. Hydraulic composition according to claim 9, further comprising from 10 to 60% by weight of sand.

11. Hydraulic composition for concrete according to any one of the claims 8 to 10, comprising: - from 2 to 15% by weight of water, - from 10 to 30% by weight of hydraulic binder comprising a cement, - from 0.05 to 3% by weight of said at least one additive, - from 10 to 60% by weight of sand and - from 10 to 60% by weight of one or more gravels.

12. A method for preparing an additive for hydraulic compositions, said additive comprising a mixture of compounds of the following formulas (I), (II) and (III): 31 in which: the groups (CH2-CH2-O) and (CH2-CH(CH3)-O) are arranged in blocks, alternately or randomly, n, n1 and n2, independently of one another, are integers which vary between 1 and 150 (inclusive), m, m1 and m2, independently of one another, are integers which vary between 0 and 150 (inclusive), with n + m ≥ 10, with n1 + m1 ≥ 1, with n2 + m2 ≥ 1, the group R is chosen from one or more of the elements H, CH3, C2H5, C3H7, C4H9, PO3X2 or the group NYZ in which: Y and Z may be identical or different, Y represents (EO)n3 – (PO)m3 – PO3X2 or (EO)n3 – (PO)m3 – H, Z represents (EO)n4 – (PO)m4 – PO3X2 or (EO)n4 – (PO)m4 – H, n3 and n4, independently of one another, are integers which vary between 1 and 150 (inclusive) and m3 and m4, independently of one another, are integers which vary between 0 and 150 (inclusive), X represents H or M and M represents a monovalent, divalent or trivalent cation, said method comprising the following steps: - oxyalkylation of the compound of formula (XIV): in the presence of at least (n1 + n2) moles of ethylene oxide and at least (m1+m2) moles of propylene oxide per mole of the compound of formula (XIV), - phosphatization of the intermediate compound of formula (XV): 32 in the presence of P2O5 and water and - optionally, partial or complete neutralization of the phosphate compound thus obtained, so as to obtain an additive comprising a mixture of the compounds of formulas (I), (II) and (III).

13. The use of an additive according to any one of the claims 1 to 7, for preparing a hydraulic composition chosen from a concrete and a mortar.

14. A method for preparing a hydraulic composition, consisting of adding an additive according to any one of the claims 1 to 7 to said composition. The present invention relates to the technical field of hydraulic compositions, for example concrete and mortar compositions. More specifically, the present patent application relates to additives used in hydraulic compositions, to the compositions containing same, and also to the method for preparing these additives and to the various uses thereof.

Field of the invention
The present invention relates to the technical field of hydraulic compositions, for example
concrete and mortar compositions. Such compositions are intended for all markets in the area
of construction. More precisely, the present patent application relates to additives used in said
hydraulic compositions.
Background of the invention
Hydraulic compositions generally comprise various chemical additives that are intended to
improve their properties. Among these, generally a chemical agent is used that has the
function of improving the state of dispersion of the mineral particles within the composition.
This chemical agent is known by various names: "dispersant", "liquefying agent",
"water reducing agent", "plasticizer" or "superplasticizer". This chemical agent makes it
possible to lower the water content of hydraulic compositions, for improving the performance
of hydraulic compositions, including mechanical strength. Other additives (for example
setting retarders or accelerators) are optionally added in parallel in the hydraulic
compositions.
There is a great variety of dispersants for hydraulic compositions. These agents vary in their
chemical composition and the properties that they induce in the compositions containing
them.
The dispersing properties of a dispersant in a hydraulic composition are evaluated by
measuring the slump, also called workability, according to standard EN 12350-2. The
workability of a concrete is an important property, which governs its placement for filling the
formwork.
It is evaluated just after it is prepared, as well as at specified times after preparation, making
it possible to evaluate the workability over time, also called slump retention, as well as the
maximum duration of workability after preparation. It will easily be understood that there is
an advantage in increasing the workability of a concrete for placement, as well as an
advantage in modulating the slump retention of hydraulic compositions, for example to
guarantee a workability for a long period (which notably allows the placement in the
formwork to be adjusted).
- 3 -
Moreover, although it is important to prolong the period of workability of a concrete, this
must not be done to the detriment of the performance of the concrete during hardening or in
the hardened state (notably the required initial or final mechanical strength), or of the level of
air entrained in the hydraulic compositions. Notably, the performance of concrete in the
hardened state is evaluated by measuring the compressive strength at different times (1, 3, 7
and 28 days).
A certain number of documents of the prior art describe the use of dispersant compounds
based on sulfonate functions -SO2O-. The inadequate efficacy of such products quickly led
the person skilled in the art to develop new structures known by the name of comb polymers.
Other documents of the prior art in fact describe the use of comb copolymers as dispersants in
hydraulic compositions. We may notably mention documents
WO 02/083594, WO 2004/094336, US 7,261,772, US 2008/087198 and
WO 2006/138017. The comb copolymers are synthetic copolymers with an anionic charge on
the skeleton and uncharged side chains. The side chains of the anionically charged comb
polymer may comprise compounds containing a polymerized epoxide, for example an
ethylene oxide, a propylene oxide and/or a 1-butylene oxide.
Documents US 2008/087198 and US 7,261,772 propose using an amide jointly with said
comb copolymers, this combination being presented as effective for dispersing mineral matter
with impurities.
As for document WO 98/58887, it proposes doping the efficacy of comb polymers in cement
matrixes containing clays, using organic or inorganic cations and quaternary (poly)amines,
optionally alkoxylated.
As for document FR 2 887 542, it recommends employing a particular cationic polymer to
neutralize the harmful effects of the clays contained in certain sands.
Document FR 2 759 704 describes the use of alkylene polyoxide compounds for dispersing
carbon black, an organic material that is amorphous, hydrophobic and not electrically
charged, different from the mineral fillers of the calcium carbonate type.
- 4 -
Document WO 97/19748 describes the use of a dispersant for dispersing pigment particles in
the paint application. This agent consists of a poly(oxyethylated) and poly(oxypropylated)
phosphate ester.
Documents FR 2 696 736, FR 2 943 053, FR 2 810 314, FR 2 763 065, WO 2012/140235 and
WO 2013/093344 describe the use of compounds bearing a polyalkoxylated chain and one or
two phosphonic amino-methylene groups as liquefying agents (or rheology extenders) for
aqueous suspensions of mineral particles. Such compounds are available commercially. As an
example, we may mention the products CHRYSO®Fluid in the Optima range (for example
Optima 100 and Optima 175).
The article by Pourchet et al. (Influence of three types of superplasticizers on
tricalciumaluminate hydration in presence of gypsum in International Conference on
Superplasticizers and other chemical admixtures in concrete, Sorrento: Italy, 2006) studies
the influence of the chemical structure of various superplasticizers, notably a
poly(oxyethylene) diphosphonate polymer, on the hydration of cement.
The inventors realized that the performances of hydraulic compositions, evaluated by the
workability of said freshly prepared composition and by the compressive strength of said
composition in the hardened state, could be improved relative to the commercially available
products of the alkoxylated diphosphonate type, by using a particular chemical additive,
namely a polyethylene glycol geminal ester phosphate according to the invention.
Brief description of the invention
An object of the present invention is to propose an additive for hydraulic compositions that
gives excellent workability after preparation, as well as an improvement in retention of
workability over time, for example after a period of 45 minutes of storage and then remixing.
Another object of the present invention is to propose an additive for hydraulic compositions
giving very good compressive strength one day after placement.
Another object of the present invention is to propose an additive for hydraulic compositions
that gives, simultaneously, retention of workability and a quick increase in strength of the
material.
- 5 -
The present invention thus relates to a chemical additive for hydraulic compositions, said
additive endowing this suspension with excellent workability after preparation, as well as
after a specified storage time (for example 45 minutes or more), as measured by the slump
test, without lowering the compressive strength value of the material obtained one day after
placement. This additive consists of a polyethylene glycol geminal mono- and diester
phosphate.
The comparative tests presented in the experimental section of the present application in fact
demonstrate the superiority of the additives according to the present invention (workability
and compressive strength) compared to products of the alkoxylated diphosphonate type,
available commercially under the name CHRYSO®Fluid in the Optima range, notably the
product Optima 100. Use of the additives according to the invention makes it possible to
increase the compressive strengths at a young age (1 day) while ensuring an improvement in
workability.
The additives according to the invention make it possible both to reduce the amount of water
required for obtaining a workable hydraulic composition and to prolong the workability of the
composition but without causing a large delay in setting.
Detailed description of the invention
Additive
A first object of the present invention consists of an additive for hydraulic compositions,
comprising a mixture of the compounds of the following formulas (I), (II) and (III):
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in which:
the groups (CH2-CH2-O) and (CH2-CH(CH3)-O) are arranged in blocks, alternately or
randomly,
n, n1 and n2, independently of one another, are integers which vary between 1 and 150
(inclusive),
m, m1 and m2, independently of one another, are integers which vary between 0 and 150
(inclusive),
with n + m ≥ 10,
with n1 + m1 ≥ 1,
with n2 + m2 ≥ 1,
the group R is chosen from one or more of the elements H, CH3, C2H5, C3H7, C4H9, PO3X2 or
the group NYZ in which:
Y and Z may be identical or different,
Y represents (EO)n3 – (PO)m3 – PO3X2 or (EO)n3 – (PO)m3 – H,
Z represents (EO)n4 – (PO)m4 – PO3X2 or (EO)n4 – (PO)m4 – H,
n3 and n4, independently of one another, are integers which vary between 1 and 150
(inclusive) and
m3 and m4, independently of one another, are integers which vary between 0 and 150
(inclusive),
X represents H or M and
M represents a monovalent, divalent or trivalent cation.
The additive according to the invention consists of a mixture of poly(ethylene glycol)
geminal ester phosphate compounds, in other words of polyethylene glycol compounds,
optionally substituted, terminated at one end with a geminal group bearing at least one ester
phosphate function. This geminal group may therefore be of the monoester phosphate or
diester phosphate type. The "geminal diester phosphate" group is also called
"gem-diphosphate" group and comprises two ester phosphates bound to one and the same
- 7 -
nitrogen atom. The "geminal monoester phosphate" group comprises an ester phosphate
group and an oxyalkylated group, these two groups being bound to one and the same nitrogen
atom. For all useful purposes, it should be noted that the "gem-diphosphate" group according
to the invention is different from the "gem-bisphosphonate" group and the "phosphonic
amino-methylene" group described in the prior art.
Thus, the compound of formula (I), a constituent of the additive according to the invention, is
a poly(ethylene glycol) geminal diester phosphate compound, whereas the compounds of
formulas (II) and (III), which may be identical or different, are poly(ethylene glycol) geminal
monoester phosphate compounds.
It is noted, for all useful purposes, in the context of the present invention, that:
- the groups represented by (CH2-CH2-O) or (O-CH2-CH2) are equivalent and may also
be represented by (EO), also called ethylene oxide,
- the groups represented by (CH2-CH(CH3)-O) or (CH(CH3)-CH2-O) or
(O- CH2-CH(CH3)) or (O-CH2-CH(CH3)) are equivalent and may also be represented
by (PO), also called propylene oxide,
- the groups EO and PO, arranged on either side of the nitrogen atom or constituting the
group R in the compounds of the present invention, are arranged in blocks, alternately
or randomly. Thus, as an example, the polyalkylene glycol chains may consist of PO
groups inserted in the middle of a cluster of EO groups or alternately the polyalkylene
glycol chains may consist of a series with a specified number of PO groups and then a
specified number of EO groups.
The additive according to the invention, or the mixture of compounds of formulas (I), (II) and
(III), may be in the form of salts, stoichiometric or not, mixed or not, and may be constituted
with alkali metals, alkaline-earth metals, amines or quaternary ammoniums.
According to one embodiment, the additive according to the invention is in acidic form.
According to another embodiment, the additive according to the invention is in neutralized
form.
- 8 -
According to yet another embodiment, the additive according to the invention is in the
partially or completely neutralized form.
When it is in the form of salts, the additive according to the invention may notably be a
calcium salt, a sodium salt or a diethanolamine salt.
According to one embodiment, the additive according to the invention is such that M is
chosen from the group consisting of the potassium ion, sodium ion, lithium ion, calcium ion,
magnesium ion, ammonium ion and a mixture of these ions.
The additive according to the invention may be in liquid form or in solid form, for example it
may be supported on a suitable support, of the mineral type (silica, fumed silica, CaCO3 etc.).
The additive according to the invention may be water-soluble or water-dispersible.
According to one embodiment, the additive according to the invention is such that, in
formulas (I), (II) and (III), n1 + m1 ≤ 10 and n2 + m2 ≤ 10.
According to another embodiment, the additive according to the invention is such that, in
formulas (I), (II) and (III), n1 and n2 are equal to 1 and m1 and m2 are equal to 0.
According to yet another embodiment, the additive according to the invention is such that, in
formulas (I), (II) and (III), R represents CH3.
According to one embodiment, the additive according to the invention is such that, in
formulas (I), (II) and (III), n varies between 10 and 120 (inclusive).
According to another embodiment, the additive according to the invention is such that, in
formulas (I), (II) and (III), n varies between 20 and 80 (inclusive).
According to one embodiment, group R in the compounds of formulas (I), (II) or (III) may
represent a linear or branched carbon chain that comprises between 1 and 4 carbon atoms
(inclusive). "Branched" is to be understood, as opposed to a linear chain, as a carbon chain
that comprises at least one substituent group on the side.
- 9 -
According to one embodiment, the present invention relates to an additive for hydraulic
compositions, comprising a mixture of the compounds of the following formulas (IV), (V)
and (VI):
in which R, n, n1, n2 and X are as defined above.
According to another embodiment, the present invention relates to an additive for hydraulic
compositions, comprising a mixture of the compounds of the following formulas (VII) and
(VIII):
in which R, n and X are as defined above.
- 10 -
The additive of formula (VII) may also be represented by the additive of the following
formula (VII'):
in which R, n and X are as defined above.
The additive of formula (VIII) may also be represented by the additive of the following
formula (VIII'):
in which R, n and X are as defined above.
According to another embodiment, the present invention relates to an additive for hydraulic
compositions, comprising a mixture of the compounds of the following formulas (IX), (X),
(XI), (XII) and (XIII):
- 11 -
in which R, n and X are as defined above.
According to this embodiment, the additive according to the invention comprises a mixture of
triphosphate, diphosphate and monophosphate compounds.
According to one embodiment of the present invention, the additive for hydraulic
compositions further comprises a compound of formula (XIX):
According to one embodiment, the additive for hydraulic compositions further comprises a
compound of formula (XIX) in an amount less than 1% by weight.
- 12 -
According to one embodiment, the additive according to the present invention further
comprises compounds (I'), (II') and (III'), of formulas identical to compounds (I), (II) and (III)
respectively, the only difference being that the group X of each of the
ester-phosphate functions represents H, the cation M or a compound of formula (I), (II) or
(III), bound to the compound by one of the hydroxyl functions of the chain
-(CH2-CH2-O)n1-(CH2-CH2(-CH3)-O)m1 or -(CH2-CH2-O)n2-(CH2-CH2(-CH3)-O)m2. Thus,
according to this embodiment, each phosphate of each ester phosphate function is able to
form two additional ester phosphate bonds.
According to one embodiment, the additive according to the present invention further
comprises compounds (IV'), (V') and (VI'), of formulas identical to compounds (IV), (V) and
(VI) respectively, the only difference being that the group X of each of the
ester-phosphate functions represents H, the cation M or a compound of formula (IV), (V) or
(VI), bound to the compound by one of the hydroxyl functions of the chain
-(CH2-CH2-O)n1 or -(CH2-CH2-O)n2. Thus, according to this embodiment, each phosphate of
each ester phosphate function is able to form two additional ester phosphate bonds.
According to one embodiment, the additive according to the present invention further
comprises compounds (VII'') and (VIII''), of formulas identical to compounds (VII) and (VIII)
respectively, the only difference being that the group X of each of the
ester-phosphate functions represents H, the cation M or a compound of formula (VII) or
(VIII), bound to the compound by one of its hydroxyl functions of the ethoxylated chain.
Thus, according to this embodiment, each phosphate of each ester phosphate function is able
to form two additional ester phosphate bonds. Thus, compound (VII'') may form up to 4
additional ester phosphate bonds and compound (VIII'') may form up to 2 additional ester
phosphate bonds.
Hydraulic composition
In the context of the present invention, a hydraulic composition is an aqueous formulation
containing water, at least one hydraulic binder and at least one additive according to the
invention. The hydraulic binder comprises at least one cement, for example a Portland
cement. We may also mention, for all useful purposes, the hydraulic binders of the calcium
aluminate cement and calcium sulfo-aluminate cement type.
- 13 -
The dosage of the additive according to the invention mainly depends on the amount of
hydraulic binders in the hydraulic composition. Most often, it is expressed in dry matter of
additive relative to the total weight of the hydraulic binder (for example cement in concrete
and mortar compositions).
According to one embodiment of the present invention, said hydraulic composition comprises
from 0.05% to 5% by dry weight of said additive relative to the dry weight of cement.
According to another embodiment of the present invention, said hydraulic composition
comprises, expressed in percentage by dry weight of said additive relative to the dry weight
of cement, from 0.1% to 3% of said additive.
This hydraulic composition is, for example, intended for making a grout, a putty, an adhesive,
a concrete or a mortar. This composition may comprise impurities, for example clays. This
composition may notably comprise latices, fibers, organic granules, inorganic granules, fillers
and/or CaCO3.
The hydraulic compositions, for example the concrete and mortar compositions, for which the
additive according to the invention may be useful, may comprise various types of cements as
hydraulic binder, such as the cements CEM I, CEM II, CEM III, CEM V as described in
standard EN 197-1. Among the latter, the cements CEM I do not comprise any additive. It is,
however, possible to add slags, fly-ash, limestone fillers and/or siliceous fillers to these
cements. The concrete compositions may be concretes of different strength grades, such as
C20/25 to C100/115.
According to one embodiment, the hydraulic composition according to the invention
comprises from 10 to 90% by weight of hydraulic binder.
According to one embodiment, the hydraulic composition according to the invention
comprises, relative to the total weight of the composition:
- from 2 to 15% by weight of water,
- from 10 to 30% by weight of hydraulic binder comprising a cement and
- from 0.05 to 3% by weight of said at least one additive.
- 14 -
According to this embodiment, the hydraulic composition according to the invention may
also further comprise from 10 to 60% by weight of sand.
According to one embodiment, the hydraulic composition according to the invention
comprises, relative to the total weight of the composition:
- from 2 to 15% by weight of water,
- from 10 to 30% by weight of hydraulic binder comprising a cement,
- from 0.05 to 3% by weight of said at least one additive,
- from 10 to 60% by weight of sand and
- from 10 to 60% by weight of one or more gravels.
The hydraulic composition according to the invention may, moreover, comprise one or more
of the following ingredients:
- sand,
- gravels,
- granules,
- fine or ultrafine fillers, for example calcium carbonate or silica,
- antifoaming agent,
- thickener,
- stabilizer,
- biocide or antibacterial agent,
- pH modifier and
- setting accelerator or retarder.
Method of manufacture of the additive according to the invention
Another object of the present invention consists of a method of manufacturing the additive
for hydraulic compositions according to the invention, by reaction between an amine and
epoxides.
More precisely, the method for preparing the additive according to the invention consists of a
step of oxyalkylation of an amine compound and then a phosphatization step of the
intermediate compound thus obtained.
- 15 -
The method of manufacturing of the additive according to the invention may be represented
according to the following mechanism, in two, optionally three, steps:
Optional neutralizing step
Additive according to formulas (I), (II) and (III)
with R, n, n1, n2, m, m1 and m2 as defined above.
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According to a first step, oxyalkylation of the primary amine compound
R-[(EO)n-(PO)m]-NH2, in which R, n and m are as defined above, is carried out in the
presence of ethylene oxide (C2H4O) and propylene oxide (C3H7O). This first step takes place
in the presence of at least (n1 + n2) moles of ethylene oxide and of at least
(m1 + m2) moles of propylene oxide. According to a second step, phosphatization of the
intermediate compounds thus obtained is carried out. According to a third optional step, the
mixture of phosphate compounds obtained is neutralized partially or completely.
Thus, the invention relates to a method for preparing an additive as defined above,
comprising the following steps:
- oxyalkylation of the compound of formula (XIV):
in the presence of at least (n1 + n2) moles of ethylene oxide and at least (m1 + m2)
moles of propylene oxide per mole of compounds of formula (XIV),
- phosphatization of the intermediate compound of formula (XV):
in the presence of P2O5 and water and
- optionally, partial or complete neutralization of the phosphate compound thus
obtained, so as to obtain an additive comprising a mixture of the compounds of
formulas (I), (II) and (III).
According to one embodiment, the method of manufacturing of the additive according to the
invention may be represented according to the following mechanism:
- 17 -
Optional neutralizing step
Additive according to formulas (IV), (V) and (VI)
with R, n, n1 and n2 as defined above.
Thus, according to this embodiment, the method for preparing an additive according to
formulas (IV), (V) and (VI) comprises the following steps:
- oxyalkylation of the compound of formula (XVI):
in the presence of at least (n1 + n2) moles of ethylene oxide per mole of compounds of
formula (XVI),
- 18 -
- phosphatization of the intermediate compound of formula (XVII):
in the presence of P2O5 and water and
- optionally, partial or complete neutralization of the phosphate compound thus
obtained, so as to obtain an additive comprising a mixture of the compounds of
formulas (IV), (V) and (VI).
-
According to another embodiment, the method of manufacturing of an additive according to
the invention may be represented according to the following mechanism:
- 19 -
Optional neutralizing step
Additive according to formulas (VII) and (VIII), or (VII’) and (VIII’)
with R and n as defined above.
Thus, according to this embodiment, the method for preparing an additive according to
formulas (VII) and (VIII) comprises the following steps:
- oxyalkylation of the compound of formula (XVI):
in the presence of at least 2 moles of ethylene oxide per mole of compounds of
formula (XVI),
- phosphatization of the intermediate compound of formula (XVIII):
in the presence of P2O5 and water and
- optionally, partial or complete neutralization of the phosphate compound thus
obtained, so as to obtain an additive comprising a mixture of the compounds of
formulas (VII) and (VIII).
According to one embodiment of the present invention, partial or complete neutralization is
carried out before the phosphatization step.
Use of the additive according to the invention
One object of the present invention consists of using an additive as described above for
preparing a hydraulic composition.
According to one embodiment, the use of this hydraulic composition additive makes it
possible to improve the workability of the hydraulic composition containing it.
- 20 -
According to this use, said hydraulic composition comprises at least one hydraulic binder, for
example a cement.
According to one embodiment, said composition is intended for preparing a concrete or a
mortar.
Other methods
The present invention also relates to a method for preparing a concrete, comprising a step
consisting of adding a suitable amount of an additive for hydraulic compositions as described
above.
The present invention also relates to a method of obtaining a hydraulic composition having a
workability over time, said method comprising a step consisting of adding a suitable amount
of an additive for hydraulic compositions as described above.
EXAMPLES
The following examples illustrate the preparation of various hydraulic compositions.
Measurements of consistency, compressive strength and capture of air are performed on these
compositions according to the following protocols.
Measurement of workability (slump) - concrete
Measurements of workability, also called measurements of slump, are carried out at room
temperature, by means of a cone without a base, of truncated shape, made of galvanized steel,
called an Abrams cone, according to standard EN 12350-2. This cone has the following
characteristics:
Top diameter: 100 ± 2 mm,
Bottom diameter: 200 ± 2 mm and
Height: 300 ± 2 mm.
The cone is placed on a plate moistened with a sponge.
The cone is then filled with a specified amount of each of the preparations. Filling takes 2
minutes. The contents of the cone are tamped using a metal rod.
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• Measurement of workability at T0
Immediately after filling, the cone is lifted vertically, which leads to slump of its contents on
the plate.
The difference in height (in mm) between the top of the cone and the upper surface of the
round disk thus constituted is measured after 30 seconds.
• Measurement of workability at T45
The concrete is left to rest for 45 minutes, the formulation is mixed again and then the
workability is measured with the Abrams cone as described above.
The difference in height (in mm) between the top of the cone and the upper surface of the
round disk thus constituted is measured after 30 seconds.
Measurement of the capture of air
Measurement of the capture of air is carried out according to standard EN 12350-7,
paragraph 3.3.
Measurement of compressive strength
This is measured according to standard EN 12390-3, paragraph 3. The compressive strength
is expressed in MPa.
Example 1
In each of the tests 1-1 to 1-4 given below, a mortar is prepared according to standard EN
196-1, by mixing with stirring: standardized sand (EN 196-1), cement (CEM I 52.5 N), water
and an additive outside the invention or according to the invention. The proportions are given
in Table 1 below.
Tests 1-1 and 1-2 (outside the invention)
These tests use one and the same additive, outside the invention, present in the mortar
composition at different concentrations (0.45% and 1.2% respectively).
This additive is based on poly(ethylene glycol) of molecular weight equal to 2,000 g/mol
phosphatized in the presence of P2O5/H2O in the following conditions:
- 260 g of PEG 2000 are weighed in an 800-ml beaker,
- 22 -
- it is heated with stirring and 18.5 g of P2O5 are added gradually in the space of about
30 minutes at a temperature of 70 (± 5)°C,
- it is left to react for 3.5h at 80 (± 5)°C,
- it is diluted by adding 273 g of water and
- it is neutralized completely with sodium by adding 32.7g of NaOH (50%).
The additive is obtained in the form of a concentrated liquid (pH = 7.5) with a dry extract of
50.3%.
Test 1-3 (outside the invention)
This test uses a dispersant outside the invention.
This agent is based on poly(ethylene glycol) of molecular weight equal to 5,500 g/mol
phosphatized in the presence of P2O5/H2O in conditions similar to those of tests 1-1 and 1-2.
The additive is obtained in the form of a concentrated liquid (pH = 7) with a dry extract of
41.5%.
Test 1-4 (according to the invention)
This test illustrates the invention and uses an additive comprising a mixture of compounds of
formulas (I), (II) and (III) in which:
- m, m1 and m2 are equal to 0,
- n = 45,
- n1 and n2 are equal to 1,
- R represents CH3 and
- X represents H.
This additive was obtained as follows:
- 310 g of compounds of the following formula are weighed in an 800-ml beaker:
in which R represents CH3 and n = 45,
- it is heated with stirring and 22 g of P2O5 are added gradually in the space of about
30 minutes at a temperature of 45 (± 2)°C,
- it is left to react for 4h at 55 (± 5)°C,
- 23 -
- it is diluted by adding 310 g of water and
- it is neutralized completely with sodium by adding 13.8 g of NaOH (50%).
The additive is obtained in the form of a concentrated liquid (pH = 7.4) with a dry extract of
53%.
Test 1-1 1-2 1-3 1-4
Outside INV Outside INV Outside INV Invention
Sand (g) 2,700 2,700 2,700 2,700
Cement (g) 900 900 900 900
Additive as is (g) 8.05 21.47 10 7.6
Water (g) 435 435 435 435
% dry additive/cement 0.45 1.20 0.45 0.45
Table 1
The workability is measured at T0 using the test described above adapted to mortar (mini-
Abrams cone) and the capture of air of each of the mortar preparations is measured. The
results obtained are presented in Table 2 below.
Test 1-1 1-2 1-3 1-4
Outside NV Outside NV Outside NV Invention
Workability T0 (mm) 100 175 140 270
Capture of air (%) 5.7 6.0 5.7 5.9
7Table 2
The best result is obtained with the additive according to the invention (test 1-4).
It gives a workability (or slump) at T0 greater than that of the mortars using an agent outside
the invention (tests 1-1 to 1-3).
Example 2
In each of the tests 2-1 to 2-3 given below, a concrete is prepared according to standard EN
480-1, by mixing with stirring: standardized sand (0/4), cement (CEM I 52.5N Holcim),
gravels 4/11 and 11/22, water and optionally an additive according to the prior art or
according to the invention. The proportions are given in Table 3 below.
- 24 -
Test 2-1 (control)
This test constitutes a control and does not use any dispersant.
Test 2-2 (prior art)
This test illustrates the prior art and uses a commercial product sold under the name
CHRYSO®Fluid Optima 100.
The dry extract of this additive is 30%.
Test 2-3 (according to the invention)
This test illustrates the invention and uses an additive comprising a mixture of compounds of
formulas (I), (II) and (III) in which:
- m, m1 and m2 are equal to 0,
- n = 45,
- n1 and n2 are equal to 1,
- R represents CH3 and
- X represents H.
The dry extract of this additive is 41%.
This additive was obtained according to a method similar to that in test 1-4.
Test 2-1 2-2 2-3
Control Prior art Invention
Sand (kg) 51.6 51.6 51.6
Gravel 4/11 (kg) 22.8 22.8 22.8
Gravel 11/22 (kg) 36.6 36.6 36.6
Cement (kg) 21 21 21
Additive as is (kg) - 0.285 0.200
Water (kg) 13.850 10.388 10.388
Water reduction - 25% - 25%
Table 3
- 25 -
The workability at T0 and at T45, the compressive strength on D1 and the capture of air of
each of the concrete preparations are measured. The results obtained are presented in Table 4
below.
Test 2-1 2-2 2-3
Control Prior art Invention
Workability T0 (mm) 200 130 180
Capture of air (%) 1.8 4.5 3.9
Workability T45 (mm) 185 0 50
Strength D1 (MPa) 7.97 10.48 14.65
Table 4
The best result is obtained with the additive according to the invention (test 2-3):
- it makes it possible to reduce the amount of water by 25% relative to the control (test 2-1),
- it makes it possible to reach a workability (or slump) at T0 greater than that of the
composition using an additive according to the prior art (test 2-2),
- in addition, it makes it possible to obtain a capture of air (synonymous with zones of
weakness in the concrete) lower than that of the composition using an additive according to
the prior art (test 2-2),
- its workability at T45 is greater than that of the composition using an additive according to
the prior art (test 2-2). Thus, the concrete has better slump retention relative to a concrete
composition using an additive according to the prior art (test 2-2) and
- it makes it possible to obtain a strength at 24h which is very significantly greater than that
of the composition using an additive according to the prior art (test 2-2).
Example 3
In each of the tests 3-1 to 3-3 given below, a concrete is prepared according to standard EN
480-1, by mixing with stirring: standardized sand (0/4), cement (CEM I 52.5N Holcim),
gravels 4/11 and 11/22, water and optionally an additive according to the prior art or
according to the invention. The proportions are given in Table 5 below.
Test 3-1 (control)
This test constitutes a control and does not use any dispersant.
- 26 -
Test 3-2 (prior art)
This test illustrates the prior art and uses a commercial product sold under the name
CHRYSO®Fluid Optima 100.
The dry extract of this additive is 30%.
Test 3-3 (according to the invention)
This test illustrates the invention and uses an additive comprising a mixture of compounds of
formulas (I), (II) and (III) in which:
- m, m1 and m2 are equal to 0,
- n = 45,
- n1 and n2 are equal to 1,
- R represents CH3 and
- X represents H.
The dry extract of this additive is 41%.
This additive was obtained according to a method similar to that in test 1-4.
Table 5
The workability at T0 and at T45, the compressive strength at D1 and the capture of air of
each of the concrete preparations are measured. The results obtained are presented in Table 6
below.
Test 3-1 3-2 3-3
Control Prior art Invention
Sand (kg) 51.6 51.6 51.6
Gravel 4/11 (kg) 22.8 22.8 22.8
Gravel 11/22 (kg) 36.6 36.6 36.6
Cement (kg) 21 21 21
Additive as is (kg) - 0.121 0.087
% dry additive/cement - 0.17 0.17
Water (kg) 13.349 11.555 11.496
Water reduction - 13.9% - 13.4%
- 27 -
Test 3-1 3-2 3-3
Control Prior art Invention
Workability T0 (mm) 195 180 195
Capture of air (%) 1.8 4.1 3.9
Workability T45 (mm) 110 0 100
Strength D1 (mPa) 6.99 9.43 10.89
Table 6
The best result is obtained with the additive according to the invention (test 3-3):
- it makes it possible to reach a workability (or slump) at T0 greater than that of the
composition using an additive according to the prior art (test 3-2),
- in addition, it makes it possible to obtain a capture of air (synonymous with zones of
weakness in the concrete) lower than that of the composition using an additive according to
the prior art (test 3-2),
- its workability at T45 is greater than that of the composition using an additive according to
the prior art (test 3-2). Thus, the concrete has better slump retention relative to a concrete
composition using an additive according to the prior art (test 3-2) and
- it makes it possible to obtain strength at D1 that is significantly greater than that of the
composition using an additive according to the prior art (test 3-2).
28
WE CLAIM :
1. An additive for hydraulic compositions, comprising a mixture of the compounds of
the following formulas (I), (II) and (III):
in which:
the groups (CH2-CH2-O) and (CH2-CH(CH3)-O) are arranged in blocks, alternately or
randomly,
n, n1 and n2, independently of one another, are integers which vary between 1 and 150
(inclusive),
m, m1 and m2, independently of one another, are integers which vary between 0 and
150 (inclusive),
with n + m ≥ 10,
with n1 + m1 ≥ 1,
with n2 + m2 ≥ 1,
the group R is chosen from one or more of the elements H, CH3, C2H5, C3H7, C4H9,
PO3X2 or the group NYZ in which:
Y and Z may be identical or different,
Y represents (EO)n3 – (PO)m3 – PO3X2 or (EO)n3 – (PO)m3 – H,
Z represents (EO)n4 – (PO)m4 – PO3X2 or (EO)n4 – (PO)m4 – H,
29
n3 and n4, independently of one another, are integers which vary between 1 and 150
(inclusive) and
m3 and m4, independently of one another, are integers which vary between 0 and 150
(inclusive),
X represents H or M and
M represents a monovalent, divalent or trivalent cation.
2. Additive according to claim 1, in which n1 + m1 ≤ 10 and n2 + m2 ≤ 10.
3. Additive according to any one of the preceding claims, according to which, in
formulas (I), (II) and (III), n1 and n2 are equal to 1 and m1 and m2 are equal to 0.
4. Additive according to any one of the preceding claims, according to which, in
formulas (I), (II) and (III), R represents CH3.
5. Additive according to any one of the preceding claims, according to which M is
chosen from the group consisting of the potassium ion, sodium ion, lithium ion,
calcium ion, magnesium ion, ammonium ion and a mixture of these ions.
6. Additive according to any one of the preceding claims, according to which, in
formula (I), m is equal to 0.
7. Additive according to any one of the preceding claims, according to which in formula
(I), n varies between 20 and 120 (inclusive).
8. A hydraulic composition comprising:
- water,
- a hydraulic binder comprising a cement and
- at least one additive for hydraulic compositions according to any one of the claims
1 to 7.
9. Hydraulic composition according to claim 8, comprising, relative to the total weight
of the composition:
30
- from 2 to 15% by weight of water,
- from 10 to 30% by weight of hydraulic binder comprising a cement and
- from 0.05 to 3% by weight of said at least one additive.
10. Hydraulic composition according to claim 9, further comprising from 10 to 60% by
weight of sand.
11. Hydraulic composition for concrete according to any one of the claims 8 to 10,
comprising:
- from 2 to 15% by weight of water,
- from 10 to 30% by weight of hydraulic binder comprising a cement,
- from 0.05 to 3% by weight of said at least one additive,
- from 10 to 60% by weight of sand and
- from 10 to 60% by weight of one or more gravels.
12. A method for preparing an additive for hydraulic compositions, said additive
comprising a mixture of compounds of the following formulas (I), (II) and (III):
31
in which:
the groups (CH2-CH2-O) and (CH2-CH(CH3)-O) are arranged in blocks, alternately or
randomly,
n, n1 and n2, independently of one another, are integers which vary between 1 and 150
(inclusive),
m, m1 and m2, independently of one another, are integers which vary between 0 and
150 (inclusive),
with n + m ≥ 10,
with n1 + m1 ≥ 1,
with n2 + m2 ≥ 1,
the group R is chosen from one or more of the elements H, CH3, C2H5, C3H7, C4H9,
PO3X2 or the group NYZ in which:
Y and Z may be identical or different,
Y represents (EO)n3 – (PO)m3 – PO3X2 or (EO)n3 – (PO)m3 – H,
Z represents (EO)n4 – (PO)m4 – PO3X2 or (EO)n4 – (PO)m4 – H,
n3 and n4, independently of one another, are integers which vary between 1 and 150
(inclusive) and
m3 and m4, independently of one another, are integers which vary between 0 and 150
(inclusive),
X represents H or M and
M represents a monovalent, divalent or trivalent cation,
said method comprising the following steps:
- oxyalkylation of the compound of formula (XIV):
in the presence of at least (n1 + n2) moles of ethylene oxide and at least (m1+m2)
moles of propylene oxide per mole of the compound of formula (XIV),
- phosphatization of the intermediate compound of formula (XV):
32
in the presence of P2O5 and water and
- optionally, partial or complete neutralization of the phosphate compound thus
obtained, so as to obtain an additive comprising a mixture of the compounds of
formulas (I), (II) and (III).
13. The use of an additive according to any one of the claims 1 to 7, for preparing a
hydraulic composition chosen from a concrete and a mortar.
14. A method for preparing a hydraulic composition, consisting of adding an additive
according to any one of the claims 1 to 7 to said composition.
The present invention relates to the technical field of hydraulic compositions, for example
concrete and mortar compositions. More specifically, the present patent application relates to
additives used in hydraulic compositions, to the compositions containing same, and also to
the method for preparing these additives and to the various uses thereof.