Plasticizer polymers with improved thermal stability
[Technical field]
5 The present invention relates to the field of polymers useful in particular as
plasticizers for aqueous suspensions of mineral particles, in particular hydraulic binders, to a
method for their preparation, to the polymers which may thereby be obtained, to the
admixture formulated from these polymers and to their use.
10 [State of the art]
The discovery of exceptional plasticizer properties of comb polymers of the
polyalkoxylated polycarboxylate (PCP) type has allowed application of screeds, mortars,
self-smoothing coatings and concretes based on increasingly performing hydraulic binders.
The use of these plasticizer polymers may prove to be delicate because of their low
15 resistance towards heat and oxidizing media. In particular, the chains of poly(alkylene oxide) tend
to degrade by oxidation when they are exposed to high temperatures and/or to an oxidizing
atmosphere. The degradation of the polymer affects its plasticizer perfonnances.
Thus, the low heat resistance of plasticizer polymers may pose problems when they are
powdered, by drying at a temperature, from the polymeric aqueous solution: degradation of the
20 polymer, or even under certain conditions a risk of explosion of the polymer powder. The limitation
of the degradation of the polymer imposes extensive precautions such as placing them under an
inert gas, CO2 or nitrogen, of the atomizing tower.
Further, these powders of plasticizer polymers have to meet the requirements for
obtaining the «transport class ». This classification, provided by the European Convention on
25 Transport of Dangerous Materials by Road (ADR) notably requires low self-heating, characterized
by the fact that a cubic sample with a side length of 100 mm has a powder temperature of less
than 200°C after exposure to a temperature of 140°C for 24 hours.
The low heat resistance of these plasticizer polymers may also impose particular
constraints for their storage. Indeed, a loss of performance may be observed after extended
30 storage of powdered polymers in a hangar where the temperature may reach 50°C over several
weeks in summer.
Finally, the low thermal resistance limits the possibilities of use of plasticizer polymers.
Thus, it is presently sought to add the plasticizer as soon as during the milling of the hydraulic
binders, notably of the cement, which is impossible with a conventional plasticizer polymer which
2
does not resist to the high temperatures and oxidizing conditions encountered during this
manufacturing step.
Several solutions have been proposed in order to improve the thermal stability of
plasticizer polymers of the polycarboxylate polyalkoxylate type and/or their resistance in an
5 oxidizing atmosphere.
From EP 1 124 892, it is thus known how to stabilize powders of polymers of the
polyalkoxylated polycarboxylate type by adding to the aqueous solution of these polymers,
anti-oxidant agents selected from phenols, amines, phosphites, thioethers and thioacids, before
drying. As these agents are generally liquid and hydrophobic, they have to be incorporated by
10 emulsification.
Because of their relative stability, these emulsions may pose specific problems during
drying. Thus, the instability of the emulsions, notably in the presence of customary additives of the
silica type, renders the management of the method delicate. The formation of deposits on the
walls of the atomizing tower is observed, which affects the quality and the yield of the method. The
15 instability of the emulsions moreover does not always give the possibility of ensuring
homogeneous distribution of the anti-oxidant agent within the polymer powder. Moreover, losses
of stabilizer by draining away with water during drying cannot be excluded. The whole of these
phenomena causes risks of heating, or even explosion, of the partly poorly protected powder.
From WO 2011/015761, associating a plasticizer with an anti-oxidant agent, as a sacrificial
20 agent, is also known in order to limit the degradation of the polymer in an oxidizing medium, for
example during the milling of the cement. Integration of certain sacrificial agents into the backbone
of the plasticizer by copolymerization, notably radical copolymerization, is also contemplated. This
method generates substantial costs since it requires a content of at least 5% by weight of
sacrificial agents in the plasticizer composition. Indeed , the proposed operating procedure seems
25 to be difficult to cany out on an industrial scale.
Generally, it is further observed that the plasticizer formulations frequently change over
time, notably by phenomena such as precipitation, coloration, viscosification, creaming, demixing,
or Ostwald ripening.
Moreover, patent application WO 2009/090471 proposes protection of a polycarboxylic
30 polymer during the esterification step by adding anti-oxidant agents, notably an aromatic amine.
These anti-oxidant agents are not intended to be integrated into the polymer and this moreover
seems to be difficult taking into account the reactivity of the described agents. Moreover, it was
observed that the method resulted in the obtaining of emulsions.
[Summary of the invention]
The object of the invention is then to propose plasticizer polymers of the polyalkoxylated
polycarboxylate type having improved stability towards heat and/or in an oxidizing medium and
5 without the drawbacks mentioned.
This object is achieved according to the invention by a polymer in which the anti-oxidant
groups are introduced into the PCP polymer by a grafting reaction. The distribution is then
homogeneous on the scale of the polymer chain, thereby giving it improved overall thermal
stabilization.
10 The powdering of these polymers by atomization from their aqueous solution may then be
carried out without any risk. The thereby obtained powder may be classified as « stable during
transport ». In addition to their excellent thermal resistance, polymers with anti-oxidant groups
according to the invention keep the same dispersing efficiency.
Also, the invention according to a first aspect is directed to a polymer comprising a main
15 hydrocarbon chain bearing carboxylic groups and polyalkoxylated chains and 0.01 to 4% by
weight of anti-oxidant groups grafted to the main chain, based on the weight of the final polymer.
Preferably, the anti-oxidant groups comprise an aromatic amine, notably an amine bearing
two aromatic substituents, moreover bearing a reactive function allowing grafting, such as 4-
aminodiphenylamine.
20 A group stemming from an anti-oxidant compound of the following fomiula (I) is particularly
prefen-ed:
wherein:
25
R1 is a hydrogen or a saturated or unsaturated, linear or branched, hydrocarbon chain or
one or more aromatic optionally fused rings, comprising from 1 to 100 carbon atoms optionally
4
intemjpted by one or more heteroatoms such as O, S, N or P; preferably R1 is a hydrogen;
R2 is identical or different and may, independently of each other, be a hydrogen or a
saturated or unsaturated, linear or branched, hydrocarbon chain, or one or more aromatic
optionally fused rings, comprising from 1 to 100 carbon atoms, optionally intermpted with one or
5 more heteroatoms such as O, S, N or P, and/or optionally substituted with one or more amine,
alcohol, ketone, halogenated derivative, isocyanate, acetoacetonate, silanol, carboxylic acid and
alcohol ester, epoxide, carbonate or mercaptan, phosphate, phosphonate, sulfate, sulfonate or
carboxylate groups; preferably R2 is a hydrogen;
F is an amine group, notably a primary amine group, an alcohol, ketone, halogenated
10 derivative, isocyanate, acetoacetonate, silanol, cariDoxylic acid and alcohol ester, epoxide,
cariDonate or mercaptan group bound to the aromatic ring optionally through a saturated or
unsaturated, linear or branched, hydrocarbon chain including up to 100 carbon atoms; preferably
F is a primary amine group.
The anti-oxidant compound is grafted on the polymer by reaction of the reactive function F
15 with a reactive function of the PCP polymer. Advantageously, the anti-oxidant group may notably
be grafted on the main chain via a carboxylic group, by means of an amide or ester bond. The
anti-oxidant group may however be also grafted through any other type of covalent bond.
The grafted polymer according to the invention preferably has a weight average molar
mass (Mw) comprised between 1,000 and 1,000,000, preferably between 5,000 and 110,000.
20 According to a pretended order, the polymer is in the fonn of powder.
Advantageously, it includes between 0.1 and 4% by weight of anti-oxidant groups, based
on the weight of the polymer.
According to a second aspect, the invention is directed to a method for preparing a
polymer comprising the step of.
25 (i) esterifying a polycarboxylic compound with an alkoxy polyalkoxyglycol in the presence
of an anti-oxidant compound which may react, under conditions of the reaction, with a reactive
function borne by the polycarboxylic compound in order to form a covalent bond between the
polycarboxylic compound and the anti-oxidant compound.
Preferably, step (i) is carried out in two distinct steps:
30 (a) the reaction medium is first brought to a temperature comprised between 50 and 95°C
and under reduced pressure;
5
(b) the reaction is then continued by heating to a temperature comprised between
100 and 200°C under reduced pressure and/or under a flow of inert gas until the end of the
reaction.
Moreover, the method may further comprise a step for powdering the obtained grafted
5 polymer.
The powdering step may then be directly carried out from the polymer stemming from step
(b). Alternatively, it may also be carried out by canying out the steps of.
- putting the obtained grafted polymer into an aqueous solution; and
- powdering the obtained polymer solution, notably by atomization, flaking with a thin film
10 on a drum or milling.
According to a third aspect, the invention is also directed to a polymer which may be
obtained by the described method. Preferably, this is such a polymer according to the invention in
the form of a notably aqueous solution or in the form of a powder.
According to a fourth aspect, the invention is directed to an admixture useful as a
15 plasticizer of suspensions of mineral particles, comprising the polymer according to the invention.
Preferably, the admixture according to the invention appears as a limpid aqueous solution.
It advantageously includes 10 to 50% by weight of polymer as well as, if necessary, additives
which are customary in this matter.
According to a fifth aspect, the invention is finally directed to the use of a described grafted
20 polymer for fluidifying suspensions of mineral particles.
According to a last aspect, the invention is directed to the use of a grafted polymer as
described for reducing the water demand of hydraulic compositions, notably cement
compositions.
It is particularly directed to this last use in which the polymer is added in liquid and/or
25 powder form before and/or during milling of the cement.
[Detailed description of the invention]
Within the scope of the present discussion, the term of « solution » is meant to cover
essentially monophasic liquid formulations. Preferably, these are limpid solutions, as
6
demonstrated by turbidity measurements carried out by means of a TUB 550 IR
turbidimeter of the WTW brand ,of less than 1,000, preferably less than 100 and most particularly
less than 50 or even 10. Aqueous solutions are particularly targeted, although they may also
include minority amounts of other solvents.
5 By the term of « grafting » is meant the modification of a polymer by reaction with a
compound different from the monomers making up the initial polymer. At the end of the grafting
reaction, the grafted compound is bound to the polymer through a covalent bond, forming a side
group. The existence of a grafted reaction may be demonstrated by the impossibility of recovering
from the reaction mixture the grafted compound by physical separation means such as extraction
10 with a solvent. The grafting of the polymer may also be demonstrated by the detection of the
thereby formed amide, ester or other bonds, for example by the appearance of absorption bands
in the respective regions in infrared spectroscopy (IR).
By the term of « suspension of mineral particles » is meant any aqueous dispersion
of a hydraulic setting binder, notably of cements such as Portland cement (CEM I and
15 cements with additions as defined by the EN-197-1 standard), aluminous cements, calcium
sulfates either anhydrous or semihydrates, addition materials with a hydraulic or pozzolanic
nature such as slags (as defined in the Cement standard NF EN 197-1 paragraph 5.2.2), for
example from blast furnaces, flying ashes (as defined in the Cement standard NF EN 197-1,
paragraph 5.2.4), natural pozzolans, calcined shales (as defined in the Cement standard NF
20 EN 197-1 paragraph 5.2.5), limestones (as defined in the Cement standard NF EN 197-1,
paragraph 5.2.6) or further silica fumes (as defined in the Cement standard NF EN 197-1,
paragraph 5.2.7) or mixtures thereof. Other additions, not presently recognized by the
Cement standard NF EN 197-1 (2001), may also be used. These are notably metakaolins,
such as metakaolins of type A according to the NFP 18-513 standard, and siliceous
25 additions such as siliceous additions of Qz mineralogy according to the NFP 18-509
standard.
The term also encompasses inert mineral fillers such as granulates, sands, calcium sulfate
dihydrates as well as calcium carbonates, or further lime hydrate, silica, titanium hydroxide, clay
compounds and metal oxides.
30 More particularly, by the term of« suspension of mineral particles » is meant any aqueous
dispersion of a hydraulic setting binder, notably of cements such as Portland Cements (CEM I and
cements with additions as defined by the E-197-1 standard), aluminous cements, calcium sulfates
either anhydrous or semihydrates, addition materials with a hydraulic or pozzolanic nature such as
blast furnace slags, flying ashes, natural pozzolans. The term also encompasses inert mineral
35 fillers such as granulates, sands, calcium sulfate dihydrates as well as calcium carbonates, or
7
further lime hydrate, silica, titanium hydroxide, clay compounds and metal oxides.
By the temri of« hydrocarbon chain » is meant a linear or branched aryl alkyl or alkyl aryl,
aromatic, saturated or unsaturated, linear or branched aliphatic group including carbon and
hydrogen atoms. Within the scope of the present invention, the hydrocarbon chain is preferably a
5 saturated linear aliphatic chain.
By the term of « anti-oxidant group » is meant any group capable when it is present in
lower concentrations than those of the units of the polymer, of being oxidized, of significantly
slowing down, or even preventing their oxidation (see Handbook of Anti-oxidants, Second Edition
by Lester Packer, Marcel Dekker, 2002, p [4]). Within the scope of this discussion it will be
10 considered that an oxidation is slowed down when the induction time, measured by differential
scanning calorimetry (DSC) as explained later on, increases by at least 100%, preferably 300%,
and most particularly 500% or more as compared with the same polymer without anti-oxidant
agent.
Preferably, these are groups resulting from the grafting of anti-oxidant compounds
15 comprising an amine, alcohol or phenol function and most particularly aromatic amines of fomnula
I as defined earlier.
By the tenn of « polycarboxylic compound », is meant a polymer or copolymer bearing
several carboxylic functions such as carboxylic acid, carboxylic anhydride, and/or optionally other
reactive functions such as an amine, alcohol, ketone, halogenated derivative, isocyanate,
20 acetoacetonate, silanol, carboxylic acid and alcohol ester, epoxide, carbonate or mercaptan
group.
According to a first aspect, the invention is directed to a polymer comprising a main
hydrocarbon chain bearing carboxylic groups and polyalkoxylated chains, characterized in that it
includes from 0.01 to 4% by weight of anti-oxidant groups grafted to the main chain, based on the
25 weight of the final polymer.
The polymers according to the invention are derived from polymers said to be « comb
polymers » including a main hydrocarbon chain on the one hand and side groups on the other
hand. More specifically, these are polyalkoxylated polycarboxylates, so-called « PCPs », which
are characterized by the presence on the main chain of carboxylic groups and of polyoxylated
30 groups as side groups. Additionally, the polymer according to the invention bears anti-oxidant
groups as side groups. In their most broad definition, the polymers according to the invention are
therefore polymers of the PCP type modified by grafting of anti-oxidant groups.
10
8
The simultaneous presence of the three types of groups gives the polymer according to
the invention interesting properties as an admixture, notably as a plasticizer for hydraulic
compositions.
Subject to not interfering in an unfavorable way with the hydration reaction of the hydraulic
composition and of course to not slowing down the oxidation reactions, the anti-oxidant groups
may be of very diverse nature.
In particular these may be groups stemming from amines, in particular aromatic amines. It
is more preferred that the anti-oxidant groups be sterically hindered groups. Also notably amines
bearing two aromatic substituents are preferred.
Preferably, the anti-oxidant compounds used for modifying the polymer fit the following
formula (I):
wherein:
R1 is a hydrogen or a saturated or unsaturated, linear or branched hydrocarbon chain, or
15 one or more aromatic optionally fused rings, comprising from 1 to 100 carbon atoms optionally
interrupted with one or more heteroatoms such as O, S, N or P; preferably R1 is a hydrogen;
R2 is identical or different and may, independently of each other, be a hydrogen or a
saturated or unsaturated, linear or branched hydrocarbon chain, or one or more aromatic
optionally fused rings, comprising from 1 to 100 cariDon atoms, optionally intenupted with one or
20 more heteroatoms such as O, S, N or P, and/or optionally substituted with one or more amine,
alcohol, ketone, halogenated derivative, isocyanate, acetoacetonate, silanol, carboxylic acid and
alcohol ester, epoxide, carbonate or mercaptan, phosphate, phosphonate, sulfate, sulfonate or
carboxylate groups; preferably R2 is a hydrogen;
F is an amine group, notably a primary amine, alcohol, ketone, halogenated derivative,
25 isocyanate, acetoacetonate, silanol, carboxylic acid and alcohol ester, epoxide, carbonate or
mercaptan group bound to the aromatic ring optionally through a saturated or unsaturated, linear
or branched hydrocarbon chain including up to 100 carbon atoms; preferably F is a primary amine
group.
Preferably, the anti-oxidant compound is an aromatic amine bearing a reactive function
with a carboxylic function, for example a primary amine or alcohol group. Amines derived from
diphenylamine such as 4-aminodiphenylamine (ADPA), p-amino-4-methyl-diphenylamine,
5 p-amino-4'-ethoxy-diphenylamine, p-amino-4'-methoxy-diphenylamine and p-amino-4'-(N,Ndimethylamino)-
diphenylamines are particularly prefen-ed. 4-aminodiphenylamine (ADPA) is most
prefen^ed.
The proportion of the anti-oxidant groups in the polymer according to the invention may
greatly vary. As this will be shown in the following, a proportion of 0.5% by weight based on the
10 weight of the polymer already allows a notable improvement in the heat resistance of the polymer.
It was observed that the resistance is even further pronounced when the polymer includes a
proportion of 1 to 2% by weight. Although the presence of anti-oxidant groups beyond 5, or even
beyond 4% by weight does not necessarily interfere with the anti-oxidant effect, it is not desirable,
notably in order to maintain the economical nature and the application properties of the product.
15 Also, the polymers according to the invention comprise 0.01 to 5% and preferably 0.01 to
4%, and in particular between 0.1 and 4% by mass of anti-oxidant groups.
The polymer according to the invention also includes as side groups, polyoxyalkylated
chains. These polyoxyalkylated chains may be bound to the main chain directly or via carboxylic
functions, notably through an ester bond.
20 These carboxylic groups may notably be in the form of a non-dissociated acid or acid
anhydride. Most often, they will however be at least partly neutralized, esterified or amidified.
The molar proportion of the free carboxylic groups in the polymer may vary from 0 to 99%,
in particular from 40 to 97%.
The grafted polymer according to the invention generally has an average molar mass
25 comprised between 1,000 and 1,000,000 (Mw), preferably between 5,000 and 110,000 (Mw) as
determined by SEC (size exclusion chromatography) in polyoxyethylene standard equivalents.
According to a second aspect, the invention proposes a method for preparing the polymer
including anti-oxidant groups as described above.
According to a prefen^ed embodiment of the invention, the polymer is prepared by an
30 esterification method, from prepolymers, said to be a « post-grafting » method. The anti-oxidant
agent is also introduced into the esterification step.
«
10
Preferably, the anti-oxidant groups are introduced with the polyoxyalkylated chains
during a single step, in what is designated as a « one pot reaction », thus making any intemnediate
isolation step unnecessary. The method may thus be conducted rapidly and inexpensively.
The grafting is preferably achieved by reaction of the reactive functions of the polymer,
5 notably the carboxylic groups, with an anti-oxidant compound bearing a reactive function, notably
an alcohol or primary or secondary amine group.
The anti-oxidant groups are preferably bound to the polymer by means of an amide or
ester function.
Also, the invention is directed to a method for preparing the polymer described above
10 comprising the step of:
(i) esterifying a polycarboxylic compound with an alkoxy polyalkoxyglycol in the presence
of an anti-oxidant compound which may react under the conditions of the reaction with a reactive
function borne by the polycarboxylic compound in order to form a covalent bond between the
polycarboxylic compound and the anti-oxidant compound.
15 The pH of the reaction mixture is advantageously weakly acid, preferably comprised
between 4 and 6.
The polycarboxylic acid may be a polymer including identical or different carboxylic units.
This is preferably a polyacrylic or polymethacrylic acid. The weight molar mass Mw of the
polycarboxylic is preferably comprised between 500 and 10,000.
20 The alkoxy polyalkoxyglycol preferably includes ethylene oxide and optionally propylene
oxide units. Several different glycols may be used advantageously. The weight molar mass Mw of
the glycol is preferably comprised between 150 and 10,000.
Preferably, the polycarboxylic acid is not entirely esterified. Also, most often an amount of
glycol of less than the one required for ensuring complete esterification of the polymer, for
25 example 1 to 40% of the number of carboxylic functions of the polymer, will be added.
Broadly, the anti-oxidant compound may be defined as comprising an anti-oxidant group
and a reactive function which may react with one of the functions of the polymer, notably a
carboxylic group, so as to thereby allow grafting. For example, an anti-oxidant compound may
bear a primary amine or alcohol function which, as a reactive function, will allow grafting on the
30 polymer by reaction with carboxylic functions of the polymer.
However, other assumptions may be contemplated, such as for example the main
11
hydrocarbon chain of the polymer may bear reactive functions of the amine, alcohol,
ketone, halogenated derivative, isocyanate, acetoacetonate, silanol, carboxylic acid and
alcohol ester, epoxide, carbonate or mercaptan type which may react with similar functions
borne by the anti-oxidant agent.
The main hydrocarbon chain of the grafted polymer will therefore be connected to the
anti-oxidant group through covalent bonds of different nature, such as:
10
15
20
An amide bond: reaction between an amine and a carboxylic acid and/or carboxylic
acid anhydride and/or acid and alcohol ester
An imide bond: reaction between an amine and a carboxylic acid anhydride
A carboxylic ester bond: reaction between an alcohol and a carboxylic acid and/or
carboxylic acid anhydride
A thioester bond: reaction between a mercaptan and a carboxylic anhydride
An ether bond: reaction between a halogenated derivative and an alcohol; reaction
between an alcohol and an epoxide
A sulfide bond: reaction between a mercaptan and an epoxide, reaction between a
mercaptan and a halogenated derivative
A urea bond: reaction between an amine and an isocyanate
A urethane bond: reaction between an alcohol and an isocyanate; reaction between a
carbonate and an amine
A mixed carbonate bond: reaction between an alcohol and a carbonate
An amine II and/or III bond: reaction between an amine I and a halogenated derivative
An imine bond: reaction between a ketone and an amine I
A ketoamide bond: reaction between an amine and an acetoacetonate
The amount of anti-oxidant compound introduced into the reaction mixture will depend on
25 the desired grafting level. Advantageously, less than 5% and preferably less than 4% by weight
based on the dry weight of polymer will be added.
Preferably, the method according to the invention is conducted so as to carry out
12
steps (i) in two distinct steps:
(a) the reaction mixture is first brought to a temperature comprised between 50 and
95°C and under reduced pressure;
(b) the reaction is then continued by heating to a temperature comprised between 100 and
5 200°C under reduced pressure until the end of the reaction.
Altematively, the carboxylic monomer may be polymerized and the carboxylic groups may
then be esterified to the desired degree with polyoxyalkylated compounds, as this is described for
example in patent application FR 2 776 285, before grafting the obtained product with an
anti-oxidant compound.
10 Preferably, the anti-oxidant compound is an alcohol or an amine bearing an
anti-oxidant group, the amines being preferred because of their better reactivity at low
temperature.
The grafting reaction may be advantageously carried out at a temperature above
120°C, preferably between 150 and 200°C, and in particular between 170 and 180X. The
15 water formed by the reaction is then removed from the reaction mixture by evaporation, and
the reaction product is recovered as a dry residue.
The carboxylic groups possibly present in the reaction product may then be totally or
partly neutralized.
According to a preferred embodiment, the polymer according to the invention appears
20 as a powder.
Preferably, the powdering is carried out from the polymer in a solution. Because of
^ the increased thermal stability of the polymer according to the inventron, the powdering may
be achieved with a customary and economical technique such as atomization in air, flaking,
for example by means of a thin film drying technique, from the polymer solution. However,
25 the polymer may also be powdered directly at the end of the synthesis, for example by milling
the molten and then cooled anhydrous polymer.
Also, according to a third aspect, the invention is directed to a polymer with an
anti-oxidant group which may be obtained by the method, object of the invention.
The polymers according to the invention may be used as such. However they are
30 advantageously powdered or formulated before use in order to facilitate transport, storage
and dosage. According to a more preferred embodiment, the polymer according to the
invention is found as a powder.
13
According to a fourth aspect, the invention proposes an admixture for
suspensions of mineral particles comprising the described polymer with anti-oxidant groups.
In order to facilitate the application and dosage thereof, the admixture may be present
in the form of a solution in a suitable solvent. Indeed, by incorporating the anti-oxidant
5 functions into the polymer, there are no longer any problems of solubilization of the
anti-oxidant, the polymer protected against oxidation is soluble and may therefore be easily
formulated as a solution. One is no longer confronted with segregation, sedimentation or
flocculation problems observed with emulsions, and storage is easy.
Preferably, the suitable solvent comprises or consists of water. In certain cases, the
10 addition of another solvent, such as an alcohol or a glycol may be contemplated additionally
or alternatively, for example for facilitating solubilization.
The polymer concentration of the admixture mainly depends on the contemplated
application. Generally, the formulation of the admixture comprises 1 to 50, preferably 10 to 40%
by weight of polymer based on the total weight.
15 By the grafting of the anti-oxidant groups, the polymer according to the invention is most
often water-soluble and forms limpid solutions which are stable over time.
Alternatively, the admixture may also be present in a dry form, notably as a powder. The
powder is made either directly from the dry polymer obtained at the end of the synthesis, or from
the polymer put into a solution.
20 Various technologies for powdering the anhydrous polymer may be used such as
tabletting and subsequent milling or flaking and subsequent milling or further spraying by cooling
the anhydrous molten polymer (spray cooling).
Various powdering technologies from the polymer in solution may be used such as
atomization, flaking with a thin film on a drum and milling. Generally, the powdering of polymers
25 from a solution is better controlled technically and often consequently justified the additional prior
step of putting the polymer in solution.
The fonnulation of the admixture may moreover comprise other customary additives, such
as anti-foam agents, accelerators, retardants, water-repellent agents, de-aerating agents, other
plasticizers, air-entraining agents or anti-foam agent stabilizers.
14
Also, the invention according to a fifth aspect proposes the use of the polymer
described above for fluidifying a suspension of mineral particles and for maintaining the
worl
380
>380
Variation of the
induction time
[%]
0
375
353
83
183
258
>533
>533
The results of these tests for the studied polymers are grouped in Table 2 above.
10
First of all, it is seen that the induction time of the polymers is substantially prolonged in
the presence of anti-oxidant compounds. More specifically, it is seen that the thermal stability of
PCP polymers increases with the grafting level of anti-oxidant agent (Examples 1 to 4) as
compared with the same PCP which does not contain any anti-oxidant agent (Reference Example
1). In fact, the variation of the induction time is very well correlated with the grafting level, which
may be explained by a good distribution of the anti-oxidant agent on the polymer.
Moreover, it is seen that the PCP polymer obtained in example 4 gives better stability than
Reference Example 2, which includes the polymer and the anti-oxidant agent in the form of an
emulsion.
15 These results also confirm that the stability of the PCP polymers grafted according to the
invention is not affected when they are powdered (see Example 4 and Example 4 with a powder)
The curve collected for the polymer of Example 4, in the form of a solution and of a
powder and of the polymer of Reference Example 2 in the form of a powder is illustrated in Fig. 4.
It is seen that the curve obtained for the powder of the polymer of Reference Example 2 shows an
21
exothermic peak, interpreted as an induction time while this peak is absent from the
recorded curves for the polymer according to the invention, whether it is in the form of a powder or
a solution.
B. Viscosity
5 The viscosity of the polymers in solution, an important parameter since it in particular
conditions the ease of dosage, was evaluated versus temperature as follows.
The polymer solution was deposited on the plane of a rheometer with a heating resistor
(BOHLIN INSTRUMENT - CVO 100) and viscosity was then measured at different temperatures
by means of a cone.
10 Fig. 2 illustrates the viscosity curves obtained for the polymers according to the invention
and according to the Reference Examples, under identical conditions, i.e. neutralized to pH 6.5
and with 40% of dry content in solution respectively.
The results show that the polymer solutions obtained according to Examples 3 and 4 have
a lower viscosity than the polymer solution according to Reference Example 1, without any
15 anti-oxidant agent.
C. Evaluation of the application performances
In order to evaluate the application performances of the polymers according to the
invention, self-spreading, viscosity, setting time and mechanical strengths of a formulation of
self-smoothing coating with as an admixture the polymers according to the invention and with
20 reference polymers respectively were evaluated.
The self-smoothing coating formulation used for the evaluation, without any polymer, is
detailed in Table 3 below. The operating procedure used is the following:
480 g of tap water are weighed in the metal tank of a Turbotest Rayneri (VMI Rayneri)
mixer provided with a V^anchor blade and then, under stin-ing at 240 rpm, the dry components
25 mixed beforehand are added within 20 seconds. The moment when the dry components are
added is the initial point for measuring time. The whole is kneaded under stirring at 800 rpm for 2
minutes.
The PCP polymer is added to the formulation in the dosage indicated in Table 4 below, to
the dry components if it is a powder, or otherwise to the mixing water.
22
Table 3: Formulation of the self-smoothing coating
Component
Aluminous cement
Calcium sulfate
Calcium carbonate
Calcium carbonate
Siliceous sand
Redispersable resin
Lithium carbonate
Tartaric acid
Cellulose ether
Anti-foam agent
W/C
Amount
[% by weight]
20
10
17.62
15.73
34.56
1.5
0.05
0.14
0.1
0.1
24%
10
C.I. Self-smoothing
Self-smoothing of the formulation of prepared coating as indicated above is measured
according to the following procedure.
After preparing the coating according to the operating procedure indicated above, a
spreading cone is laid at the center of a glass plate and the cone is then filled to the brim at due
times, 3, 7 and 20 minutes after the beginning of the kneading.
The cone is then lifted up delicately to the vertical and drained off for a few instants before
measuring the spreading over 3 diagonals after stabilization of the flow (after about 3 mins). The
average of the 3 measurements is retained as a result (result expressed in mm). If required, any
particularity of the spreading, of the aspect of the mortar in the bowl, is observed (e.g.:
penetration, segregation).
15
The results obtained for the fonnulations of coatings with polymer admixture according to
Example 4 and with reference polymers 1 and 3 at a dosage of 0.2% and 0.05% are grouped in
Table 4 below.
23
Table 4: Self-spreading of a coating formulated with addition of a PCP polymer
EXAMPLE
Ref1
Ref3
EX 4
Refl
Ref3
EX 4
Dosage *
0.2
0.2
0.2
0.05
0.05
0.05
Self-spreading
3mins
155
160
160
160
150
158
7 mins
160
160
160
155
150
160
15 mins
160
160
162
155
150
160
20 mins
160
160
160
155
150
150
25 mins
160
160
160
145
145
150
* in % by weight based on the total dry material.
It is seen that the self-spreading values at a dosage of 0.2% are equivalent and remain
stable for 25 minutes for the reference polymer 1 (polymer without any anti-oxidant agent) and the
polymer according to Example 4. These results indicated that grafting with an anti-oxidant agent
does not affect the performances in terms of self-spreading.
Equivalent performances with the polymer according to the invention are also observed at
a dosage of 0.05%, as compared with the polymer according to Reference Example 3 (polymer
added with anti-oxidant agent).
10 The results concerning the coatings prepared with the polymer according to the invention
as a powder are collected together in Table 5 below. It is seen that the obtained powder from the
grafted polymer does not affect the self-spreading values as compared with the powder obtained
from an emulsion, the measured values being equivalent.
24
Table 5: Self-spreading of a cement coating with a PCP polymer admixture
EXAMPLE
Reference
Example 2
(powder)
Example 4
(powder)
Dosage *
0.03
0.05
0.1
0.2
0.03
0.05
0.1
0.2
Self-spreading
3mins
116
141
145
148
107
146
150
150
7 mins
123
144
150
150
126
151
155
155
15 mins
ND
ND
ND
ND
ND
ND
ND
ND
20 mins
130
148
152
147
126
153
155
157
25 mins
ND
ND
ND
ND
ND
ND
ND
ND
C.2. Viscosity of the coating
In order to compare the effect of the polymers according to the invention on the viscosity
of the coating, the viscosity was evaluated versus the shear gradient of coatings with admixture
with a dosage of 0.2% according to the following procedure.
10
The behavior of the coatings at different steps of the practical duration of use of the mortar
once it is mixed, may be described by a flow profile measurement. This type of measurements
with variable rate gradients in particular gives the possibility of following the rheological behavior of
the product during the hydraulic settings. Indeed, certain domains of rate gradients are directly
representative of the behavior of the products during its storage, its pumping, or further of its
manageability.
15
The rheological behavior of a self-smoothing coating with the composition indicated in
Table 3 above is determined in the following way: 300 g of self-smoothing mortar are mixed with
the rated water level in a 0.5 L pot (d = 9 cm) by means of an IKA mixer provided with an 8 cm
blade for 3 minutes at 800 rpm. About 7 minutes after the beginning of the mixing, the viscosity
and the stress are measured by carrying out a rate gradient scan from 0.1 to 1,000 s"^ by means
25
of a rheometer (Rheomat RM260, marketed by Mettler Toledo) with a cylindro-conical
geometry MS DIN 145.
Before the measurement, all the samples are subject to a same mechanical stress, i.e.
pre-shearing at 50 s"^ for 10 seconds, in order to position them in a comparable structuration
5 condition. The rate gradients are selected on a logarithmic scale, and the measurements are
carried out step by step at rate gradients of 0.1, 0.2, 0.5, 1, 2, 5, 10, 20, 50, 100, 200 and 500 s"''
and then from 500 to 0.1 s"^ via the same measurement sequence. Further, in order to take into
account the impact of the rate gradient on the time required for obtaining rheological equilibrium,
longer measurement times are used for low rate gradients, in order to ensure that rheological
10 equilibrium is reached. After preliminary evaluation, the retained measurement times are: 20
seconds for rate gradients of 0.1, 0.2 and 0.5 s\ 10 seconds for gradients of 1, 2 and 5s"\ 20
seconds for gradients of 10, 20 and 50 s"\ and 5 seconds for gradients of 100, 200 and 500 s"Ten viscosity measurements are carried out for each rate gradient. The result is given by
the average of these values.
15 The obtained results are grouped in Fig. 3. It is seen that the viscosity of the coatings
formulated with a polymer without any anti-oxidant agent (Reference Example 1) is substantially
equivalent to that of such a coating formulated with a polymer according to Example 4. This
observation indicates that the grafting of the polymer with an anti-oxidant agent does not affect the
performance of the polymer as regards viscosity.
20 C.3. Setting time and mechanical strength
The values of setting time and the mechanical flexural and compression strength were
also evaluated for the formulations of self-smoothing coating with admixture, as studied above.
The setting time was determined according to the test with the fall of a Vicat needle as
described in the NF EN 196-3 standard. The results are indicated in Table 6 below.
25 For the purpose of determining the strength of the obtained mortar, test specimens
were prepared as follows. After preparing the mortar as described above, measurement test
specimens are made in metal molds with dimensions of 2 x 2 x 16 cm. The hardened test
specimens are removed from the mold 2 hours before mixing and kept at 23 ± 2°C and 50 ±
5 %RH until the measurement times.
30 The 3-point flexural mechanical strength was detennined according to an Ibertest press
with a 3-point flexure device, for which the rise in load is set to 50N/s +/-10N/S. The test specimen
26
is placed and centered on the device, the unformed surface is perpendicular to the
supporting points. The test is then started with the following parameterization:
Section C1 = 20 mm Square C2 = 20 mm
Base length = 100 mm Contact rate 5= 5%
The compression strength was determined on prismatic test specimens in an Ibertest
press with compression for prismatic test specimens, the strength slope was set to 2,400N/s +/-
200N/S. From both half-specimens of the flexion test, the test specimen is placed and centered on
the device, the unformed surface is perpendicular to the supporting plate. The test is then started
with the following parameterization:
10 Section CI = 20 mm Square C2 = 40 mm
Base length = 100 mm Contact rate 5= 15%
Table 6: Setting time and mechanical strength
15
EXAMPLE
Refl
Ref3
EX 4
Setting
[min]
Begin.
64
57
71
time
End
73
61
79
IVIechanical
strength
[MPa]
2h
2.4
2.9
2.3
flexural
24h
3.8
4.6
3.8
Mechanical
compression strength
[MPa]
2h
11.6
13
11.8
24h
20.8
24.2
18.8
The flexural and compression strength results are averaged for a same measurement due
time. The respective result for the polymer according to Example 4 as compared with polymers
according to Reference Example 1 (without any anti-oxidant agent) and Reference Example 3
(mixed with an anti-oxidant agent) are summarized in Table 6 above.
The setting time was also studied for formulating the self-smoothing coating prepared by
using the polymer as a powder, for different dosages. The results are grouped together in Table 7
below.
20
27
Table 7: Setting time for different dosages
EXAMPLE
Reference
Example 2
(powder)
Example 4
(powder)
Dosage *
0.03
0.05
0.1
0.2
0.03
0.05
0.1
0.2
Setting time [min]
Beginning
54
59
72
103
67
65
81
100
End
60
65
78
112
73
71
84
106
The obtained results show that the grafting of the PCP polymer with an anti-oxidant agent
does not notably affect the setting time or the flexural and compression strength of the hardened
5 material. Moreover it is seen that these advantages are also obtained when the polymer according
to the invention is used as a powder and this over a wide range of dosages.
The results above moreover show that the grafting does not affect the application
properties such as the viscosity of the formulation, the setting time and the flexural and
compression mechanical strength.
10 The polymers according to the invention therefore provide the possibility of having
dispersing polymers with improved thermal stability at a lower cost.
C.4. Water demand of cements with grafted PCP as an admixture before milling
15
In order to evaluate the strength of the polymers according to the invention at the
temperature of the cement during the milling, the water demand of milled cements in the presence
of polymers according to the invention was evaluated. As a comparison, the same test was also
28
carried out with a non-grafted polymer. A cement prepared without any polymer was
used as a control.
A cement CEM I was milled by means of a heated ball milling machine after incorporating
2,000 ppm of a polymer solution, expressed in % by dry weight based on the weight of cement.
The milling was carried out in a heated milling machine with Blaine fineness around 4,000 g/cm^.
The cement was then maintained for 3 hours at 100°C.
10
Table 8: Water demand according to EN 196-3 of a milled cement with an admixture
EXAMPLE
Control
Ref. 1
EX.4
W/C
0.218
0.220
0.213
The prepared cement samples were then respectively mixed with the required amount of
water for obtaining a same plasticity according to French standard EN 196-3. The ratio between
the amount of water and the amount of cement is called the W/C ratio.
The results are summarized in Table 8 above. It is seen that the water demand is not
affected when a non-protected PCP is added to the clinker before milling. On the other hand,
when a PCP according to the invention, grafted with anti-oxidant groups, is added to the cement, it
is seen that the water demand decreases, indicating the effective presence of a plasticizer. From
15 these results it may be infen'ed that the grafted polymer according to the invention preserved its
capability of reducing water even after having been exposed to the oxidizing medium at a high
temperature for an extended time.
In fact, the polymer according to the invention gives the possibility of obtaining a cement
with improved water demand (lower W/C) of about 5% for Example 4 as compared with
20 Reference Example 1.
As a conclusion, the combined presence, in the polymers with anti-oxidant groups
according to the invention, of long polyoxyalkylated chains having a plasticizing effect, and of
anti-oxidant groups having a capability of suppressing or slowing down the oxidation of
oxidizing agents seems to be at the origin of the particular properties of the polymer
25 according to the invention. These polymers including described anti-oxidant groups are
therefore particulariy of interest as a plasticizer of hydraulic compositions notably cement
compositions.
29
Because of their stability towards heat and oxidation, the polymers according
to the invention may be incorporated into compositions based on a hydraulic binder, notably
cements even before milling, without any thermal degradation during the process, in order to
give them specific properties (prefluidified cements, stability of the cements during storage,
5 decrease in the water demand of the cements). Preparing a mixture as a powder with a
hydraulic binder may thus be contemplated in order to propose an organomineral powder
easy to apply and stable during storage.
Moreover they are soluble and may therefore be easily formulated as a solution,
notably as an aqueous solution, which avoids problems of segregation, sedimentation or
10 flocculation observed with emulsions. The solutions are limpid, stable and not very viscous
and allow easy storage and ease of use.
The solubility of water and the heat and oxidation resistance facilitate the
transformation of the polymers according to the invention, since the powdering may be
achieved in an easy and economical way, notably by atomization in air and therefore without
15 requiring them to set under an inert gas of the atomization tower.
Because of their stability towards heat and/or oxidation, these polymers may further
be transported, stored and mixed, including as a powder, without any risk. In particular, it is
possible to obtain transport classification for these compounds.
Moreover, the polymers according to the invention, as this has been demonstrated,
20 impart the expected fluidifying effect and mechanical properties at the same level as that of
comparable non-stabilized polymers.
C.5. Comparison of the spreading of non-grafted and grafted PCPs
In order to demonstrate the stabilizing effect of the grafting with anti-oxidant groups, a
cement before milling received an admixture with a PCP or a same grafted PCP and then the
25 performances of mortars prepared from these cements were compared.
REFERENCE EXAMPLE A
Polymer not grafted with an anti-oxidant agent
Into a four-neck flask, provided with a stirrer and connected to a water pump,
30 241.49 g of polymethacrylic acid in a 30% aqueous solution and then 1.64 g a 50% by weight
30
sodium hydroxide aqueous solution were introduced. In the medium, were then
introduced 758.2 g of methoxypolyethylene glycol with a weight average molar mass
Mw=5,000. The reaction mixture was brought to a temperature of 80°C. At this stage, the
medium is limpid. A vacuum is gradually applied to the whole until a pressure is obtained of
5 about 50 mbars and the temperature of the reaction medium is then gradually brought to
165°C.
The reaction was continued for a period of 4 hours counted from the moment when
the reaction medium attained 160-165''C at a pressure of 50 mbars. The progress of the
esterification reaction is followed by the dosage of unreacted MPEG, by GPC, by comparing
10 the area of the peak with a calibration curve established beforehand. The reaction is stopped
when the residual MPEG level represents less than 2% of the reaction mass.
At the end of the reaction, the reaction medium is brought back to atmospheric
pressure and heating is cut off. Once the temperature of the reaction medium is less than
90°C, the molten polymer is diluted to 50% with 637.9 g of water. 300.2 g of polymer solution
15 are diluted with 321.3 g of water and the pH is then brought to 6.5 with 4.51 g of 50% sodium
hydroxide solution. The final extract is at 25.1%.
REFERENCE EXAMPLE B
Polymer not grafted with an anti-oxidant agent
20 In a jacketed glass reactor, provided with a stirrer and connected to a vacuum pump,
1,761.8 g of polymethacrylic acid in a 30% aqueous solution followed by 11.15 g of a 50% by
mass sodium hydroxide aqueous solution are introduced. Into the medium, were then
introduced 2,230.1 g of methoxypolyethylene glycol with a weight average molar mass
Mw=2,000. The reaction mixture was then brought to a temperature of 80°C. At this
25 stage, the medium is limpid. Vacuum is gradually applied to the whole down to a pressure of
about 50 mbars and the temperature of the reaction medium is then gradually brought to
165X.
The reaction was continued for a period of 4 hours counted from the moment when
the reaction medium attains 160-165°C at a pressure of 50 mbars. The progress of the
30 esterification reaction is followed by dosage of unreacted MPEG, by GPC, by comparing the
area of the peak with a calibration curve established beforehand. The reaction is stopped
31
when the residual MPEG level represents less than 2% of the reaction mass.
At the end of the reaction, the reaction medium is brought back to atmospheric
pressure and the heating is cut off. Once the temperature of the reaction medium is less than
90°C, the molten polymer is diluted to 50% with 2,553 g of water, 340.1 g of polymer solution
5 are diluted with 362.3 g of water and the pH is then brought to 6.5 with 10.2g of 50% sodium
hydroxide solution. The final extract is at 21.9%.
EXAMPLE A
Polymer of Reference Example A grafted with an anti-oxidant agent
Into a four-neck flask, provided with a stirrer and connected to a water pump,
10 241.49 g of polymethacrylic acid in a 30% aqueous solution and then 1.64g of a 50% by
weight sodium hydroxide aqueous solution were introduced. In the medium, were then
introduced 758.2 g of methoxypolyethylene glycol with a weight average molar mass
Mw=5,000. The reaction mixture was brought to a temperature of 80°C. At this stage, the
medium is limpid. 16.7 grams of 4-aminodiphenylamine, i.e. 2% by weight based on the
15 weight of dry polymer, are introduced into the reactor and very rapidly pass into the solution.
A vacuum is gradually applied to the whole down to a pressure of about 50 mbars and the
temperature of the reaction medium is then gradually brought to 165°C.
The reaction was then continued for a period of 4 hours counted from the moment
when the reaction medium attained 160-165°C at a pressure of 50 mbars. The progress of
20 the esterification reaction is followed by the dosage of unreacted MPEG, by GPC, by
comparing the area of the peak with a calibration curve established beforehand. The reaction
is stopped when the residual MPEG level represents less than 2% of the reaction mass.
At the end of the reaction, the reaction medium is brought back to atmospheric
pressure and heating is cut off. Once the temperature of the reaction medium is less than
25 90°C, the molten polymer is diluted to 50% with 632.6 g of water. 340.1 g of polymer solution
are diluted with 362.3 g of water and the pH is then brought to 6.5 with 3.02 g of a 50%
sodium hydroxide solution. The final extract is at 21.7%.
EXAMPLE B
Polymer of Reference Example B grafted with an anti-oxidant agent
30 Into a jacketed glass reactor, provided with a stirrer and connected to a vacuum
32
pump, 1761.8 g of polymethacrylic acid in a 30% aqueous solution followed by 11.15g of
a 50% by mass sodium hydroxide aqueous solution were introduced. Into the medium, were
then introduced 2,230.1 g of methoxypolyethylene glycol with a weight average molar mass
Mw=2,000. The reaction mixture was brought to a temperature of 80°C. At this stage, the
5 medium is limpid. 54.8 g of 4-aminodiphenylamine, i.e. 2% by weight based on the weight of
dried polymer, are introduced into the reactor and very rapidly pass into the solution. A
vacuum is gradually applied to the whole down to a pressure of about 50 mbars and the
temperature of the reaction medium is then gradually brought to 165°C.
The reaction was continued for a period of 4 hours counted from the moment when
10 the reaction medium attains 160-165°C at a pressure of 50 mbars. The progression of the
esterification reaction is followed by dosage of unreacted MPEG, by GPC, by comparing the
area of the peak with a calibration curve established beforehand. The reaction is stopped
when the residual MPEG level represents less than 2% of the reaction mass.
At the end of the reaction, the reaction medium is brought back to atmospheric
15 pressure and the heating is cut off. 19.4 g of this anhydrous polymer are diluted in 71.5 g of
water and the pH is then brought to 6.5 with 1.1 g of a 50% sodium hydroxide solution. The
final extract is at 21.7%.
MILLING OF THE CEMENT
A cement CEM I consisting of 95% by mass of clinker and of 5% of gypsum was milled by
20 means of a heated ball mill after incorporating 1,200 ppm of polymer solution, expressed in
dry mass % based on the cement weight, to the materials before milling. The milling as
carried out at 105°C by adjusting the number of revolutions in order to obtain Blaine fineness
close to 3,500 g/cm^. 5 kg of material are milled in each operation, the milling load, consisting
of balls with a diameter from 13 to 30 mm, is 60 kg. The Blaine fineness is measured
25 according to the EN 196-6 standard. The fluidifying power, also called water reducing power,
of the polymer subject to milling is measured on a mortar prepared according to the
operating procedure described on page 12 of the Lafarge patent WO2011015761. The
spreading is measured for 5 mins after preparing the mortar according to the EN 1015-3
standard « Determination of the consistency of a fresh mortar with a vibrating table »: the
30 wider the spreading, the greater the fluidifying power of the polymer.
Table 9 below groups the evaluations which were carried out:
33
Table 9: Evaluation of the spreading for non- grafted polymers and polymers grafted with
anti-oxidant groups
Blaine
fineness
(cm'/g)
Total number
of revolutions
T5 spreading
(mm)
Reference
example A
3422
1700
205
Example A
3492
1800
260
Reference
example B
3547
1600
230
Example B
3528
1600
265
The results show that the spreading is significantly greater for polymers grafted with an
anti-oxidant group, according to the invention, as compared with polymers of equivalent
structure but without any anti-oxidant.
These results demonstrate a favorable effect due to the grafted anti-oxidant, and may be
related to a protective effect of anti-oxidant groups, giving the possibility of avoiding
degradation of the polymer.
10
34
CLAIMS no 950 14?
1. A polymer comprising a main hydrocarbon chain bearing carboxylic groups and
polyalkoxylated chains, characterized in that it includes 0.01 to 4% by weight based on the
weight of the final polymer, of anti-oxidant groups grafted to the main chain.
2. The polymer according to claim 1, characterized in that it includes between 0.1 and
4% by weight of anti-oxidant groups, based on the weight of the polymer.
3. The polymer according to claim 1 or 2, characterized in that the anti-oxidant groups
comprise an aromatic amine.
4. The polymer according to one of claims 1 to 3, characterized in that the anti-oxidant
15 group stems from a compound of the following formula (I):
wherein:
R1 is a hydrogen or a saturated or unsaturated, linear or branched hydrocariDon chain or
one or more aromatic optionally fused rings, comprising from 1 to 100 carbon atoms optionally
20 intemjpted with one or more heteroatoms such as O, S, N or P; preferably R1 is a hydrogen;
R2 is identical or different and may independently of each other, be a hydrogen or a
saturated or unsaturated, linear or branched hydrocarbon chain, or one or more aromatic
optionally fused rings, comprising from 1 to 100 carbon atoms, optionally intermpted with one or
more heteroatoms such as O, S, N or P, and/or optionally substituted with one or more amine,
25 alcohol, ketone, halogenated derivative, isocyanate, acetoacetonate, silanol, carboxylic acid and
alcohol ester, epoxide, cariDonate or mercaptan, phosphate, phosphonate, sulfate, sulfonate or
cariDOxylate groups; preferably R2 is a hydrogen;
F is an amine group, notably a primary amine, an alcohol, ketone, halogenated derivative.
ORIGINAL
•
35 \M' 10
isocyanate, acetoacetonate, silanol, carboxylic acid and alcohol ester, epoxide, carbonate or
mercaptan group bound to the aromatic ring optionally through a saturated or unsaturated, linear
or branched hydrocarbon chain including up to 100 cariaon atoms; preferably F is a primary amine
group.
5
5. The polymer according to one of claims 1 to 4, characterized in that the
anti-oxidant group is grafted to the main chain via a carboxylic group, by means of an amide
or ester bond.
10 6. The polymer according to one of claims 1 to 5, characterized in that it has a weight
average molar mass comprised between 1,000 and 1,000,000, preferably between 5,000
and 110,000 (Mw).
15
7. The polymer according to one of claims 1 to 6, as a powder.
8. A method for preparing a polymer according to one of the preceding claims,
comprising the step of:
(i) esterifying a polycarboxylic compound with an alkoxy polyalkoxyglycol in the
presence of an anti-oxidant compound which may react under conditions of the reaction with
20 a reactive function borne by the polycarboxylic compound in order to form a covalent bond
between the polycarboxylic compound and the anti-oxidant compound.
9. The method according to claim 8, wherein the step (i) is carried out in two distinct
steps:
25 (a) the reaction mixture is first brought to a temperature comprised between 50 and
95°C and under reduced pressure;
(b) the reaction is then continued by heating to a temperature comprised between
100 and 200°C under reduced pressure and/or under a flow of inert gas until the end of the
reaction.
30
10. The method according to claims 8 or 9, further including a step for powdering the
obtained grafted polymer.
11. The method according to claim 10, wherein the powdering step is directly carried
35 out from the polymer stemming from step (b).
u
36
RIGINAL
00 q50« \ &
FEB lOW
12. The method according to claim 10, wherein the powdering step comprises
the steps of:
- putting the obtained grafted polymer in an aqueous solution; and
- powdering the obtained polymer solution, notably by atomization, flaking through a
5 thin film on a drum or milling.
13. A polymer, characterized in that it is obtainable by the method according to one of
claims 8 to 12.
10 14. An admixture useful as a plasticizer of suspensions of mineral particles
comprising the polymer according to one of claims 1 to 7 or 13.
15. The admixture according to claim 14, as a limpid aqueous solution.
15 16. The admixture according to claim 15, including from 10 to 50% by weight of
polymer as well as customary additives if necessary.
17. The use of a polymer according to one of claims 1 to 7 or 13 for fluidifying
suspensions of mineral particles.
20
18. The use of a polymer according to one of claims 1 to 7 or 13 for reducing the
water demand of hydraulic compositions.
19. The use according to claim 18, wherein the polymer is added in liquid form and/or
25 as a powder before and/or during milling of a cement.