Method For Inerting Clays In Sands For The Preparation Of Hydraulic Compositions
Abstract:
The invention concerns a composition useful for inerting clays in hydraulic compositions, comprising at least 50 wt. % of a cationic polymer having a cationic charge density more than 0. 5 meq/g and an intrinsic viscosity less than Idl/g, as active substance.
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5, IMPASSE DES TILLEULS, F-381110 SAINT JEAN DE SOUDAIN (FR)
Specification
The present invention relates to a composition which is
advantageous for inerting harmful impurities, such as clays,
in hydraulic compos, it ions.
It is sometimes difficult to control the properties of
hydraulic compositions in a consistent manner. The quality of
the raw materials is often the cause of these variations. In
particular, it has been found that sands, or more
particularly the impurities which are contained in sands,
such as clays, can bring about fluctuations in the properties
of hydraulic compositions.
In some cases, these fluctuations are due to a decrease in
the efficacy of plasticisers of the polymer type having a
comb structure, also referred to as superpLasticisers.
According to document WO 98/58887, the absorption of these
polymers by swelling clays of the 2:1 type present in sands
is the cause of this decrease in efficacy. It is known to
eliminate clays and other impurities from sands by means of
washing in water. The dirty water is then processed using a
flocculatlon agent which allows the liquid/solid separation
to be accelerated and thus allows clean water to be recovered.
This water is then recycled in order' to wash the sand again.
However, this solution is costly in terms of equipment and
requires a substantial supply of water. Furthermore, the
washed sands generally contain residual flocculant which has
negative effects on the properties of the hydraulic
compositions.
The application JP 9-221346 proposes neutralising the
negative effect of the residual flocculant of the anionic
polymer type by adding a cationic polymer.
Another solution involves not separating the clays from the
sands, but instead iherting the clays in the sands. Document
WO 98/58687 proposes the use of agents which modify the
activity of the clay, for example, by reducing the absorption
capacity thereof or by carrying out a pre-absorption
operation. The document proposes, inter alia, the use of
organic or inorganic cations, including quaternary
(poly)amines which may be alkoxylated.
However, the agents described are still not entirely
satisfactory in terms of efficiency. It is thus necessary to
add a large measure of agents in order to process materials
which have a significant content in terms of impurities. A
large measure results in costs which render the method
disadvantageous on an industrial scale.
Furthermore, in contrast to the teaching of document WO
98/58887, different clays, of the type 1:1, for example, can
also bring about a decrease in the quality of the hydraulic
compositions.
The object of the present invention is therefore to provide a
composition useful for reducing the undesirable effects
linked to the presence of harmful impurities, such as clays.
In particular, such a composition is sought which is robust,
that is to say, effective for different hydraulic
compositions. Furthermore, a composition is sought which is
stable during storage, inexpensive and whose use does not
require sophisticated equipment.
This object is achieved by a, composition comprising a
specific eationic polymer. Preferably, the specific cationic
polymer is associated with an anionic polymer.
In this manner, the invention relates mainly to a composition
useful for inerting clays in hydraulic compositions
comprising at least 50% by weight of a catioiiic polymer which
has a density of cationic charges which is greater than 0.5
me<3/9 s-hd an intrinsic viscosity which is less than 1 dl/g as
an active substance.
In the context of this description, the term "polymer" is
intended to refer to a compound which comprises more than two
monomeric units which may be identical or different and which
may or may not have a specific order.
The term "cationicity" is intended to refer to the density of
positive charges which are carried by a compound. The
cationicity can be measured by means of colloidal titration.
The term "intrinsic viscosity" is intended to refer to the
limit value of the reduced viscosity r\i / c with infinite
dilution of the polymer. This value is linked to the mean
molecular weight of a polymer.
The term "hydraulic composition" is intended to define any
composition which has hydraulic setting, and quite
particularly mortars and concretes which are intended for all
construction markets (building works, civil engineering or
prefabrication sites).
The terra "sand" is intended to define granulates having a
mean gra'nulometric size of between 0 and 6 mm, preferably
between 0 and 4 mm. They may be of any mineral, calciferous,
siliceous or siliceous limestone type, or any other type.
This definition also includes fillers or other specific
inorganic substances which are likely to be present in
hydraulic compositions.
The term "clays" is intended to. refer to aluminium and/or
magnesium silicates, in particular phyllosilicates having a
lamellar structure, which are typically spaced with
approximately from 7 to approximately 14 Angstr6ms. However,
this term also refers to clays of other types, in particular
amorphous clays. Clays which are commonly found in sands
include in particular montmorillonite, illite, kaoliriite,
muscovite and chlorite. Clays may be of the 2:1 type but also
of the 1:1 type (kaolinite) or 2:1:1 type (chlorite).
The term "active substance" is intended to refer to the
constituents of the composition which have, an effect on the
properties of the hydraulic composition, excluding
constituents which form the carrier, in particular the
solvents or dispersing agents, emulsifiers and other
additives.
The invention is based on the finding that eationic polymers
which have a specific density of cationic charge and
molecular weight, preferably in association with anionic
polymers, are particularly effective for inerting the
impurities in hydraulic compositions.
According to the invention, the cationic polymer which is
advantageous for optimising the inerting effect has &
cationieity greater than 0.5 meg/g, preferably greater than
meg/g, and in particular greater than 2 meg/g.
According to the invention, the cationic polymer further has
a molecular weight which is expressed by an intrinsic
viscosity less than 1 dl/g, preferably leas than 0.8 dl/g,
and in particular less than 0.6 dl/g.
Advantageously, the composition comprises, at least 50% by
weight, and in particular at least 70%, and guite
particularly from 70 to 80% by weight of cationic polymer.
The cationic polymer may have a linear, comb or branched
structure. Preferably, the cationic polymer is linear.
Cationic groups may be in particular phosphdnium, pyridinium,
sulphonium and quaternary amine groups, the last ones being
preferred. These cationic groups may be located in the chain
of the polymer or as a pendant group.
A large number of cationic polymers are known per se.
Polymers of this type may be obtained directly using one of
the known methods of polymerisation, such as radical
polymerisation, polycondensation or polyaddition.
They may also be prepared by means of post-synthetic
modification of a polymer, for example, by means of grafting
groups which carry one or moTe cationic functions to a
polymer chain which carries appropriate reactive groups.
The polymerisation is carried out starting with at least one
monomer which carries a cationic group or an appropriate
precursor thereof.
Polymers obtained from monomers carrying amine and inline
groups are particularly advantageous. Nitrogen can be
quatcruised after polymerisation in known manner, for example,
by means of alkylation using an alkylating compound, for
example, with methyl chloride, or in an acid medium, by means
of prbtonation.
Cationic polymers containing cationic groups of quaternary
amine are particularly appropriate.
Monomers which already carry a cationic quaternary amine
function may include in particular the salts of
diallyldialkyl ammonium, quaternised (meth)acrylates of
dialkylaminoalkyl and {meth)acrylamides N-substicuted by a
quaternised dialkylaminoalkyl.
The polymerisation can be carried out with non-ionic monomers,
preferably having a short chain, comprising from 2 to 6 atoms
of carbon. Anionic monomers may also be present so long as
they do not affect the cationic groups.
In the context of the modification of polymers by means of
grafting, it is possible to mention grafted natural polymers,
such as cationic starches.
Advantageously, the cationic polymer contains groups whose
cationic character is present only in an acid medium.
Tertiary amine groups, which are cationic by means of
protonation in an acid medium, are particularly preferred.
The absence of ionic nature in hydraulic compositions of the
concrete or mortar type having an alkaline pH further renders
them robust with regard to other ionie, in particular anionic,
compounds.
By way of example, it is possible to mention cationic
polymers from the polyvinylamine family which can be obtained
by means of polymerisation of N-vinylformamide, followed by
hydrolysis. Quaternised polyvinylamines may be prepared as
described in the patent US 5,292,441. Polymers of the
polyethyleneimine type are also suitable. The latter are
quaternised by means of protonation.
Particularly preferred are the cationic polymers obtained by
means of polycondensation of epichlorohydrin with a mono or
dialkylamine, in particular methylamine or dimethylamine.
Their preparation is described, for example, in patents US
3,738,945 and US 3,725,3.12.
The cationic polymer unit obtained by means of
polycondensation of dimethylamine and epichlorohydrin can be
represented as follows:
""Me
Me HO
cie
Also appropriate are polymers of the polyacrylamide type
modified by means of a Mannich reaction, such as
polyacrylamide N- substituted, by a dimethylaminomethyl group.
Also appropriate are cationic polymers which are obtained by
means of polycondensation of dicyandiamide and formaldehyde
These polymers and the method for obtaining them are
described in the patent FR 1 042 084 .
The invention thus also relates to a method for inerting
clays in sands which are intended for the preparation of
hydraulic compositions, wherein during the production of the
sand, the sand is placed in contact with a polymer obtainable
by condensation of dicyandiamide with formaldehyde,
optionally in the presence of other compounds.
According to a preferred embodimenti the polymer is
obtainable by condensation of dicyandiamide with formaldehyde
in the presence of:
A) a polyalkylene glycol, and/or
B) a polyalkoxylated polycarboxylate; and/or
C) an ammonium derivative.
The exact chemical constitution of the polymer obtained in
this manner is not known precisely. It will therefore be
described below substantially using the preparation method
thereof.
Method of preparation
The polymer is obtainable by condensation of dicyandiamide
with formaldehyde, optionally in the presence of other
compounds, in particular a polyalkylene glycol (A) , a
polyalkoxylated polycarboxylate (B) and/or a qu.aternisation
agent (C>.
The condensation reaction between dicyandiamide and
formaldehyde requires 2 moles of formaldehyde for 1 mole of
dicyandiamide, according to the following reaction diagram
(Figure Removed)
In this manner, the molar ratio between formaldehyde and
dicyandiamide is preferably in the range of from 0.8:1 to 4:1,
in particular from 1:1 to 3:1. A molar excess greater than 4
does not provide any additional advantage, but may lead to an
undesirable setting of the reaction mixture.
It ia particularly preferred to carry out the reaction with a
Slight stdichiometric excess of formaldehyde, with a molar
ratio between formaldehyde and dicyandiamide in the range of
2.2:1 to 2.8:1.
Preferably, the polymer is obtained by means of condensation
of formaldehyde with dicyandiamide in the presence of
additional compounds. This allows the properties of the
polymer to be adjusted, in particular the solubility thereof
in water and the affinity thereof with respect to clays.
The polyalkylene glycol (compound A) is preferably a compound
having the formula (I):
R2-0-[R1-0]n-R3
where:
R1 is an alkyl group of Ci to C4, preferably an ethyl and/or
propyl group;
R2 and R3 are, independently of each other, a hydrogen atom
or an alkyl group of :Ci to C4, preferably a methyl group,- and
n is a number from 25 to 1000.
By way of example, it may be polyethylene glycol,
polypropylene glycol, a copolymer of ethylene oxide/propylene
oxide or an admixture of these different compounds.
Preferably, it is polyethylene glycol.
The molecular weight of the compound A is preferably from
1000 to 35000.
viscosity measurements have shown that the presence of the
compound A modifies the structure of the polymer formed and
the efficiency levels thereof.
The quantity of compound A optionally used in the reaction is
in principle leas than that of the main react ants
dicyandiamide and formaldehyde.
In this manner, the reaction admixture generally contains
from 0 to 10%, preferably from 0.5 to 3, and quite
particularly from 0.8. to 1% by weight of compound A.
The polyalkoxylated polycarboxylate (compound B) is a comb
polymer which comprises a main hydrocarbon chain to which
both lateral carboxylic groups and alkoxylated groups are
connected, in particular groups of propylene oxide (PO) ,
ethylene oxide groups (EG) and/or combinations thereof. The
lateral groups may be ionic or non-ionic. It is preferably a
compound having the following formula {ID :
(Figure Removed)
where:
R1 and R2 are, independently of each other, a hydrogen atom
or a methyl group;
R3 and R4 are, independently of each other, an alkylene group
of Ci to C