Dispersing polymers with improved thermal stability

Abstract

The invention relates mainly to a polymer comprising a hydrocarbon-based main chain bearing carboxylic groups and polyalkoxylated chains and up to 4% by weight of anti-oxidant groups, relative to the weight of the final polymer, grafted to the main chain. It also relates to a method for preparing such a polymer and to an admixture which is of use as a plasticizer of suspensions of mineral particles comprising same. Finally, it is related to the use of such a polymer for fluidifying suspensions of mineral particles and reducing the water demand of hydraulic compositions.

Claims

1. A polymer comprising a main hydrocarbon chain bearing carboxylic groups and polyalkoxylated chains, and comprising 0.01 to 4% by weight, based on the weight of the final polymer, of antioxidant groups grafted to the main chain.

2. The polymer according to claim 1, comprising between 0.1 and 4% by weight of antioxidant groups, based on the weight of the polymer.

3. The polymer according to claim 1, wherein the antioxidant groups comprise an aromatic amine.

4. The polymer according to claim 1, wherein the antioxidant group stems from a compound of the following formula (I): ##STR00003## wherein: 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 interrupted with one or more heteroatoms; 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 interrupted with one or more heteroatoms, 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; F is an amine group, an alcohol, ketone, halogenated derivative, 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 comprising up to 100 carbon atoms.

5. The polymer according to claim 4, wherein said heteroatom is O, S, N or P.

6. The polymer according to claim 4, wherein R1 is hydrogen.

7. The polymer according to claim 4, wherein said heteroatom is O, S, N or P.

8. The polymer according to claim 4, wherein R2 is hydrogen.

9. The polymer according to claim 4, wherein the amine group is a primary amine group.

10. The polymer according to claim 1, wherein the antioxidant group is grafted to the main chain via a carboxylic group, by means of an amide or ester bond.

11. The polymer according to claim 1, wherein the polymer has a weight average molar mass of between 1,000 and 1,000,000 (Mw).

12. The polymer according to claim 1, as a powder.

13. A method for preparing a polymer according to claim 1, comprising the step of: (i) esterifying a polycarboxylic compound with an alkoxy polyalkoxyglycol in the presence of an antioxidant compound, which may react under conditions of the reaction with a reactive function born by the polycarboxylic compound in order to form a covalent bond between the polycarboxylic compound and the antioxidant compound.

14. The method according to claim 13, wherein the step (i) is carried out 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 200 C. under reduced pressure and/or under a flow of inert gas until the end of the reaction.

15. The method according to claim 13, further comprising a step for powdering the obtained grafted polymer.

16. The method according to claim 15, wherein the powdering step is directly carried out from the polymer stemming from step (b).

17. The method according to claim 15, 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 thin film on a drum or milling.

18. A polymer obtainable by the method according to claim 13.

19. A method of plasticizing a suspensions of mineral particles comprising adding to said suspension of mineral particles an admixture comprising the polymer according to claim 1.

20. The method according to claim 19, wherein the admixture is a limpid aqueous solution.

21. The method according to claim 20, wherein the admixture comprises from 10 to 50% by weight of the polymer.

22. A method of fluidifying a suspension of particles comprising adding to the suspension of particles a polymer according to claim 1.

23. A method of reducing water demand of a hydraulic composition comprising adding to said hydraulic composition a polymer according to claim 1.

24. The method according to claim 23, wherein the polymer is added in liquid form and/or as a powder before and/or during milling of a cement.

25. The polymer according to claim 1, wherein the polymer has a weight average molar mass of between 5,000 and 110,000 (Mw).

Description

SHORT DESCRIPTION OF THE FIGURES

(1) The appended figures show:

(2) FIG. 1: a differential scanning calorimetry curve (DSC) of a polymer, the arrow indicating the induction time;

(3) FIG. 2: the viscosity versus temperature of solutions of PCP polymers according to Examples 3 and 4 and according to Reference Examples 1 and 2;

(4) FIG. 3: viscosity versus the rate gradient of a formulation of self-smoothing coating with as an admixture, a PCP polymer according to Example 4 and according to Reference Example 1 and 3; and

(5) FIG. 4: a differential scanning calorimetry curve (DSC) of the polymer of Example 4, as a powder and as a solution, and of the polymer of Reference Example 2 as a powder.

EXAMPLES

Reference Example 1

PCP Polymer without any Anti-Oxidant Agent

(6) Into a heated four-neck flask, provided with a stirrer and connected to a water pump, 100 g of polymethacrylic acid in a 30% aqueous solution are introduced and then 0.64 g of a 50% by weight sodium hydroxide aqueous solution. Into the medium were then introduced 68.9 g (5.6% molar of the carboxylic functions of polymethacrylic acid) of methoxylated poly(ethylene oxide) with a weight average molar mass Mw=3,800. 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 down to a pressure of about 50 mbars and the temperature of the reaction medium is then gradually brought to 175 C.

(7) The reaction is continued for a period of 2 hours counted from the moment when the reaction medium attained 170-175 C. at a pressure of 50 mbars. The progression of the esterification reaction is monitored by dosage of unreacted MPEG by GPC, by comparing the area of the peak with a calibration curve established beforehand.

(8) At the end of the reaction, the reaction medium is brought back to atmospheric pressure and heating is cut off. At this stage, the presence of insoluble particles is visible. Once the temperature of the reaction medium is less than 90 C., the molten polymer is diluted to 50% by weight in water and then neutralized to pH 6.5 by means of a sodium hydroxide solution and brought back to 40% of dry extract.

Reference Example 2

PCP Polymer Mixed with an Anti-Oxidant Agent (Emulsion)

(9) The polymer in solution and neutralized to pH 6.5 obtained in Reference Example 1 is mixed with 0.35% by weight, based on dry weight of polymer, of ADDITIN RC7135 (mixture of diphenylamine derivatives marketed by Rhein Chemie, Germany) and then diluted to 35%. An emulsion is obtained.

Reference Example 3

PCP Polymer Mixed with an Anti-Oxidant Agent (Solution)

(10) The polymer in solution and neutralized to pH 6.5 obtained in Reference Example 1 is mixed with 2% by weight of 4-aminodiphenyl amine (CAS No. 101-54-2) based on the dry weight of polymer. A solution is obtained containing a few insolubles.

Example 1

Polymer Grafted with an Anti-Oxidant Agent

(11) Into a heated four-neck flask, provided with a stirrer and connected to a water pump, 100 g of polymethacrylic acid in a 30% aqueous solution are introduced and then 0.64 g of a 50% by weight sodium hydroxide aqueous solution. Into the medium, were then introduced 68.9 g (5.6 molar of the carboxylic functions of polymethacrylic acid) of methoxylated poly(ethylene oxide) with a weight average molar mass Mw=3,800. The reaction mixture was then brought to a temperature of 80 C. At this stage, the medium is limpid. 0.5 g of 4-aminodiphenylamine, i.e. 0.5% by weight based on the weight of dry polymer, are introduced into the reactor and very rapidly pass into the solution. A vacuum is gradually applied until a pressure of about 50 mbars is attained. At the end of the distillation of rds of the water, the medium is brought back to atmospheric pressure. The temperature of the reaction medium is then gradually brought to 175 C. while continuing distillation of the water. At 170-175 C., vacuum is re-applied gradually until a pressure of about 50 mbars is attained.

(12) The reaction was continued for a period of 2 hours counted from the moment when the reaction medium attained 170-175 C. at a pressure of 50 mbars. The progression of the esterification reaction is monitored by dosage of unreacted MPEG, by GPC, by comparing the area of the peak with a calibration curve established beforehand.

(13) At the end of the reaction, the reaction medium is brought back to atmospheric pressure and the heating is cut off. No formation of insoluble grains is visible at this stage.

(14) Once the temperature of the reaction medium is less than 90 C., the molten polymer is diluted to 50% by weight in water and then neutralized to pH 6.5 by means of a sodium hydroxide solution and reduced to 40% of dry extract. The obtained polymer solution is limpid with no insoluble.

Examples 2-4

Polymer Grafted with an Anti-Oxidant Agent (Variation of the Grafting Level)

(15) Example 1 is repeated according to the same operating procedure except for replacement of the amount of amine introduced as an anti-oxidant agent as indicated in Table 1 below. The obtained polymer solutions are limpid with no insoluble.

(16) The 4-aminodiphenylamine content in the polymer solutions was measured by means of the following test: 1) Diluting a known amount of product in 200 mL of water. 2) Adjusting the pH of the aqueous solution to a value of 9. 3) Triple extraction with 300 mL of ethyl acetate respectively. 4) Collecting the organic phases and washing with 2200 mL of water. 5) Evaporation of the solvent in the rotavapor. 6) Taking up the solid residue in 100 g of ethanol and dosage with HPLC by means of a preliminary calibration.

(17) The residual 4-aminodiphenylamine content of the polymer solution of Example 4, thereby measured, is 0.02% by weight based on the weight of dry polymer. Taking into account the fact that the initial amine content was 2% based on the weight of dried polymer, this result demonstrates a quasi complete reaction of the amine.

(18) Moreover, it is seen that the residual amine content does not vary for different pHs (extraction pH of 9 and 13), which backs up the assumption of a covalent bond established from the amine to the polymer.

(19) TABLE-US-00001 TABLE 1 Grafting level of anti-oxidant agent Amount of anti-oxidant agent Grafting level Grafting level EXAMPLE [g] [molar %*] [% by weight**] 1 0.5 0.80 0.50 2 0.75 1.30 0.75 3 1 1.70 1 4 2 3.30 2 Ref. 1 Ref. 2 0.35 Ref. 3 2.0 *carboxylic functions **based on the weight of dry polymer

(20) A. Evaluation of the Thermal Stability

(21) The thermal stability of the polymers obtained according to the Examples was evaluated by means of differential scanning calorimetry (DSC) in air and compared with that of the polymer of Reference Example 1. The same test was carried out for evaluating the thermal stability of polymers in the form of a powder.

(22) The powders of the polymers were prepared by atomization of an aqueous solution of the polymer according to Example 4 and to Reference Example 2 (PCP mixed with an anti-oxidant agent in an emulsion), respectively.

(23) The polymer samples from the solution were prepared by depositing the polymer solution as a film on a glass plate and then drying it in an oven. The dry film of polymer was then removed from the plate by scraping and then introduced into cups specific to differential calorimetry.

(24) Differential calorimetry is then carried out under the following conditions:

(25) Rise from 25 C. to 190 C.-2 C. per minute and maintaining 190 C. for 5 hours.

(26) Air flow rate: 60 ml/min

(27) As an indicator of thermal stability, on the differential calorimetric curve, the elapsed time is measured before the exothermic decomposition peak appears, a so-called induction time, indicated by the arrow in FIG. 1.

(28) TABLE-US-00002 TABLE 2 Thermal stability at 190 C. Variation of the Induction time induction time EXAMPLE [min] [%] Ref. 1 60 0 Ref. 2 285 375 Ref. 2 (powder) 272 353 EX. 1 110 83 EX. 2 170 183 EX. 3 215 258 EX. 4 >380 >533 EX. 4 (powder) >380 >533

(29) The results of these tests for the studied polymers are grouped in Table 2 above.

(30) 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.

(31) 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.

(32) 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)

(33) 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 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.

(34) B. Viscosity

(35) 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.

(36) The polymer solution was deposited on the plane of a rheometer with a heating resistor (BOHLIN INSTRUMENTCVO 100) and viscosity was then measured at different temperatures by means of a cone.

(37) 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.

(38) 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 anti-oxidant agent.

(39) C. Evaluation of the Application Performances

(40) 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 reference polymers respectively were evaluated.

(41) 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:

(42) 480 g of tap water are weighed in the metal tank of a Turbotest Rayneri (VMI Rayneri) mixer provided with a -anchor blade and then, under stirring at 240 rpm, the dry components 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.

(43) 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.

(44) TABLE-US-00003 TABLE 3 Formulation of the self-smoothing coating Amount Component [% by weight] Aluminous cement 20 Calcium sulfate 10 Calcium carbonate 17.62 Calcium carbonate 15.73 Siliceous sand 34.56 Redispersable resin 1.5 Lithium carbonate 0.05 Tartaric acid 0.14 Cellulose ether 0.1 Anti-foam agent 0.1 W/C 24%

(45) C.1. Self-Smoothing

(46) Self-smoothing of the formulation of prepared coating as indicated above is measured according to the following procedure.

(47) 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.

(48) 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).

(49) The results obtained for the formulations 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.

(50) TABLE-US-00004 TABLE 4 Self-spreading of a coating formulated with addition of a PCP polymer Self-spreading EXAMPLE Dosage * 3 mins 7 mins 15 mins 20 mins 25 mins Ref 1 0.2 155 160 160 160 160 Ref 3 0.2 160 160 160 160 160 EX 4 0.2 160 160 162 160 160 Ref 1 0.05 160 155 155 155 145 Ref 3 0.05 150 150 150 150 145 EX 4 0.05 158 160 160 150 150 * in % by weight based on the total dry material.

(51) 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.

(52) 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).

(53) 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.

(54) TABLE-US-00005 TABLE 5 Self-spreading of a cement coating with a PCP polymer admixture Self-spreading EXAMPLE Dosage * 3 mins 7 mins 15 mins 20 mins 25 mins Reference 0.03 116 123 ND 130 ND Example 2 0.05 141 144 ND 148 ND (powder) 0.1 145 150 ND 152 ND 0.2 148 150 ND 147 ND Example 4 0.03 107 126 ND 126 ND (powder) 0.05 146 151 ND 153 ND 0.1 150 155 ND 155 ND 0.2 150 155 ND 157 ND

(55) C.2. Viscosity of the Coating

(56) 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.

(57) 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.

(58) 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.sup.1 by means of a rheometer (Rheomat RM260, marketed by Mettler Toledo) with a cylindro-conical geometry MS DIN 145.

(59) Before the measurement, all the samples are subject to a same mechanical stress, i.e. pre-shearing at 50 s.sup.1 for 10 seconds, in order to position them in a comparable structuration 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.sup.1 and then from 500 to 0.1 s.sup.1 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 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.sup.1, 10 seconds for gradients of 1, 2 and 5 s.sup.1, 20 seconds for gradients of 10, 20 and 50 s.sup.1, and 5 seconds for gradients of 100, 200 and 500 s.sup.1.

(60) Ten viscosity measurements are carried out for each rate gradient. The result is given by the average of these values.

(61) 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.

(62) C.3. Setting Time and Mechanical Strength

(63) 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.

(64) 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.

(65) 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 2216 cm. The hardened test specimens are removed from the mold 2 hours before mixing and kept at 232 C. and 505% RH until the measurement times.

(66) The 3-point flexural mechanical strength was determined 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 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:

(67) Section C1=20 mm Square C2=20 mm

(68) Base length=100 mm Contact rate 5=5%

(69) 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:

(70) Section C1=20 mm Square C2=40 mm

(71) Base length=100 mm Contact rate 5=15%

(72) TABLE-US-00006 TABLE 6 Setting time and mechanical strength Setting Mechanical Mechanical time flexural strength compression strength [min] [MPa] [MPa] EXAMPLE Begin. End 2 h 24 h 2 h 24 h Ref 1 64 73 2.4 3.8 11.6 20.8 Ref 3 57 61 2.9 4.6 13 24.2 EX 4 71 79 2.3 3.8 11.8 18.8

(73) 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.

(74) 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.

(75) TABLE-US-00007 TABLE 7 Setting time for different dosages Setting time [min] EXAMPLE Dosage * Beginning End Reference 0.03 54 60 Example 2 0.05 59 65 (powder) 0.1 72 78 0.2 103 112 Example 4 0.03 67 73 (powder) 0.05 65 71 0.1 81 84 0.2 100 106

(76) 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 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.

(77) 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.

(78) The polymers according to the invention therefore provide the possibility of having dispersing polymers with improved thermal stability at a lower cost.

(79) C.4. Water Demand of Cements with Grafted PCP as an Admixture Before Milling

(80) 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 carried out with a non-grafted polymer. A cement prepared without any polymer was used as a control.

(81) 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.sup.2. The cement was then maintained for 3 hours at 100 C.

(82) TABLE-US-00008 TABLE 8 Water demand according to EN 196-3 of a milled cement with an admixture EXAMPLE W/C Control 0.218 Ref. 1 0.220 EX. 4 0.213

(83) 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.

(84) 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 these results it may be inferred 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.

(85) 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 Reference Example 1.

(86) 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 according to the invention. These polymers including described anti-oxidant groups are therefore particularly of interest as a plasticizer of hydraulic compositions notably cement compositions.

(87) 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, 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.

(88) 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 flocculation observed with emulsions. The solutions are limpid, stable and not very viscous and allow easy storage and ease of use.

(89) 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 requiring them to set under an inert gas of the atomization tower.

(90) 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.

(91) Moreover, the polymers according to the invention, as this has been demonstrated, impart the expected fluidifying effect and mechanical properties at the same level as that of comparable non-stabilized polymers.

(92) C.5. Comparison of the Spreading of Non-Grafted and Grafted PCPs

(93) 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 performances of mortars prepared from these cements were compared.

Reference Example A

Polymer not Grafted with an Anti-Oxidant Agent

(94) Into a four-neck flask, provided with a stirrer and connected to a water pump, 241.49 g of polymethacrylic acid in a 30% aqueous solution and then 1.64 g 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. A vacuum is gradually applied to the whole until a pressure is obtained of about 50 mbars and the temperature of the reaction medium is then gradually brought to 165 C.

(95) 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 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.

(96) 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 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

(97) 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 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 165 C.

(98) 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 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.

(99) 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 are diluted with 362.3 g of water and the pH is then brought to 6.5 with 10.2 g of 50% sodium hydroxide solution. The final extract is at 21.9%.

Example A

Polymer of Reference Example A Crafted with an Anti-Oxidant Agent

(100) Into a four-neck flask, provided with a stirrer and connected to a water pump, 241.49 g of polymethacrylic acid in a 30% aqueous solution and then 1.64 g 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 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.

(101) 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 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.

(102) 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 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

(103) Into a jacketed glass reactor, provided with a stirrer and connected to a vacuum pump, 1761.8 g of polymethacrylic acid in a 30% aqueous solution followed by 11.15 g 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 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.

(104) 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 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.

(105) At the end of the reaction, the reaction medium is brought back to atmospheric 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%.

(106) Milling of the Cement

(107) A cement CEM I consisting of 95% by mass of clinker and of 5% of gypsum was milled by 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.sup.2. 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 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 EN1015-3 standard <<Determination of the consistency of a fresh mortar with a vibrating table>>: the wider the spreading, the greater the fluidifying power of the polymer.

(108) Table 9 below groups the evaluations which were carried out:

(109) TABLE-US-00009 TABLE 9 Evaluation of the spreading for non-grafted polymers and polymers grafted with anti-oxidant groups Reference Reference example A Example A example B Example B Blaine 3422 3492 3547 3528 fineness (cm.sup.2/g) Total number 1700 1800 1600 1600 of revolutions T5 spreading 205 260 230 265 (mm)

(110) 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.

(111) 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.