REACTIVE POLYACRYLIC COMPOSITION

Abstract

The invention relates to a composition for preparing a (poly)ester compound or a (poly)amide compound. This composition comprises an α-sulfonated (meth)acrylic polymer, a monofunctional or polyfunctional reactive compound, and a sulfocarboxylic acid. The invention also relates to the preparation of a (poly)ester compound or a (poly)amide compound using this composition.

Description

Title of the invention: REACTIVE POLYACRYLIC COMPOSITION

[0001] The invention relates to a composition for preparing a (poly)ester compound or a (poly)amide compound. This composition comprises an α-sulfonated (meth)acrylic polymer, a monofunctional or polyfunctional reactive compound, and a sulfocarboxylic acid. The invention also relates to the preparation of a (poly)ester compound or a (poly)amide compound using this composition.

[0002] Many technical fields utilize ester compounds or amide compounds prepared from a (meth)acrylic polymer. These compounds can be prepared from monofunctional reactive compounds comprising a single hydroxyl group or a single amine group. They can also be prepared from polyfunctional compounds comprising at least two hydroxyl or amine groups.

[0003] Typically, ester or amide formation occurs during a heated and catalyzed reaction. Known effective catalysts include phosphorus, particularly phosphorus in oxidation states I, III, or V. Reducing or eliminating a phosphorus catalyst could be compensated for by increasing the reaction temperature. However, such a temperature increase can lead to a significant degradation in the efficiency of ester or amide formation. High temperatures can lead to decarboxylation of the (meth)acrylic polymer and even to the degradation of the reactants and reaction products. The formation of degradation byproducts or colored byproducts, particularly due to excessive exposure to high temperatures, must be reduced or avoided.

[0004] Ester- or amide-forming compositions, particularly cross-linkable compositions, should exhibit high reactivity. They should allow for high reaction kinetics. Indeed, it is always advantageous to have better control over the kinetics of ester- or amide-forming reactions.

[0005] Furthermore, the esters or amides should be able to be prepared in the absence of any compound that could be considered environmentally harmful or in the absence of any compound whose use is restricted by regulations. In particular, the preparation of these compounds in the absence of any compound containing phosphorus should be preferred, especially the absence of phosphorus in oxidation states I, III, or V.

[0006] Ester or amide compounds can possess many properties that are particularly advantageous in their fields of application. However, these properties can be improved or degraded depending on the conditions under which the ester or amide compounds are prepared.

[0007] Poly(ester) or poly(amide) compounds can be used in applications requiring structural or insulating properties. In particular, these crosslinkable polymers can be applied to a material in the form of fibers or particles, especially glass or rock, or even organic material fibers, for example, organic optical fibers. These polymers can also be used to produce coatings, including water-repellent coatings or coatings providing mechanical, physicochemical, or chemical protection.

[0008] Poly(ester) or poly(amide) compounds can also be used in fields requiring dispersion properties of hydrophobic organic substances or dispersion of solid mineral substances insoluble in water.

[0009] Poly(ester) or poly(amide) compounds can also be used for the preparation of anode compositions, in particular compositions comprising carbon or a metal. After crosslinking, these compositions allow the carbon or metal particles to be fixed to a metallic substrate. The bonding strength is therefore crucial when manufacturing an anode using these anode compositions.

[0010] Prior art ester preparation compositions or aids do not always provide satisfactory solutions. Therefore, there is a need for improved compositions for the preparation of a (poly)ester compound or for the preparation of a (poly)amide compound. The invention provides a solution to all or part of the problems with prior art compositions for the preparation of a (poly)ester compound or for the preparation of a (poly)amide compound.

[0011] The invention provides an aqueous composition R comprising:

[0012] a. at least one α-sulfonated polymer A prepared in water by a polymerization reaction of at least one monomer M selected from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid and their combinations, in the presence of at least one initiator compound and at least one sulfur compound T comprising sulfur in oxidation state IV, b. at least one compound B selected from a sulfocarboxylic acid, a salt of sulfocarboxylic acid and their combinations, present in a molar quantity greater than 2% relative to the molar quantity of sulfur IV, c. at least one compound C selected from a monofunctional compound Cl selected from monoalcohols and monoamines, a polyfunctional compound C2 selected from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), sugars and glycosides and combinations of compounds Cl and C2.

[0013] Essentially, according to the invention, polymer A is an α-sulfonated polymer. It It therefore includes a sulfonated group in a terminal position. Preferably according to the invention, polymer A is selected from an α-co-disulfonated Al polymer, an α-monosulfonated A2 polymer, and combinations thereof. Polymer Al thus comprises a single sulfonated group at one of its terminal positions, while polymer A2 comprises a sulfonated group at each of its two terminal positions.

[0014] Essentially for the invention, the preparation of the polymer A is carried out by means of the monomer M. Preferably according to the invention, the monomer M is chosen from acrylic acid, a salt of acrylic acid and their combinations or a combination of acrylic acid or a salt of acrylic acid with methacrylic acid or with a salt of methacrylic acid.

[0015] According to the invention, monomer M can be combined with at least one other monomer, preferably another monomer selected from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid, and combinations thereof. In combination with another monomer, monomer M can be selected from acrylic acid, an acrylic acid salt, and combinations thereof.In combination with another monomer, the amount by weight of the other monomer is less than the amount by weight of monomer M. Preferably according to the invention, monomer M is acrylic acid alone.

[0016] Essentially, the polymer A is prepared during a polymerization reaction of the monomer M in the presence of a sulfur compound T comprising sulfur(IV). Preferably, the sulfur compound T is selected from lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, calcium di(hydrogen sulfite), magnesium di(hydrogen sulfite), and combinations thereof. Preferably according to the invention, the compound T is a monohydrogen sulfite. The preferred sulfur compound T is sodium hydrogen sulfite, also known as sodium bisulfite.

[0017] Preferably according to the invention, the molar quantity of sulfur compound T, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of monomers used. More preferably, the molar quantity of sulfur compound, preferably the molar quantity of sulfur IV, is between 1% and 15%, of preference between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used.

[0018] Preferably, the polymerization reaction is carried out at a temperature above 30°C and below 100°C, preferably below 90°C, more preferably below 80°C or 75°C. Preferably, in the polymerization reaction, the initiating compound is chosen from a peroxide (e.g. hydrogen peroxide), a hydroperoxide (e.g. tert-butyl hydroperoxide), a persulfate (e.g. sodium persulfate, ammonium persulfate, potassium persulfate), their combinations and their combinations with a metal salt, preferably a metal salt chosen from an iron salt (e.g. Fe II or Fe III), a copper salt (e.g. Cu I or Cu II) and their combinations.

[0019] Preferably, polymer A has a weight-average molecular weight Mw (measured by CES) of less than 20,000 g / mol, preferably less than 15,000 g / mol, less than 10,000 g / mol, more preferably less than 7,000 g / mol or less than 6,000 g / mol. Polymer A generally has a weight-average molecular weight Mw (measured by CES) greater than 1,000 g / mol or greater than 1,200 g / mol.

[0020] Preferably, polymer A has a polymolecularity index IP (measured by CES) of less than 4 or ranging from 1.2 to 4 or from 1.5 to 4; from 1.2 to 3 or from 1.5 to 3; from 1.2 to 2.5 or even from 1.5 to 2.5.

[0021] According to the invention, the molecular weight or mass of polymer A is determined by Size Exclusion Chromatography (SEC). A test portion of the polymer solution, corresponding to 90 mg of dry matter, is introduced into a 10 mL bottle. Mobile phase, supplemented with 0.04% dimethylformamide (DMF), is added up to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCCU: 0.05 mol / L, NaNCU: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3: 0.03 wt%. The CES chain consists of a Waters 510 type isocratic pump, with a flow rate set at 0.8 mL / min, a Waters 717+ sample changer, a furnace containing a 6 cm long and 40 mm internal diameter Waters Guard Column Ultrahydrogel pre-column, followed by a 30 cm long and 7.8 mm internal diameter Waters Ultrahydrogel linear column.Detection is performed using a Waters RI 410 differential refractometer. The oven is heated to 60°C and the refractometer to 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standard Service with peak molecular weights between 1000 g / mol and 1.106 g / mol and polymolecularity indices between 1.4 and 1.7. The calibration curve is linear and takes into account the correction obtained using [the appropriate method / method]. The flow marker was dimethylformamide (DMF). Chromatogram acquisition and processing were performed using PSS WinGPC Scientific v 4.02 software. The resulting chromatogram was integrated into the area corresponding to molecular weights greater than 250 g / mol.

[0022] According to the invention, polymer A may be non-neutralized, partially neutralized, or totally neutralized. Preferably, polymer A is non-neutralized. According to the invention, the carboxyl groups of polymer A may be partially neutralized to a degree of 70 to 97 mol%, preferably to a degree of 90 to 95 mol%. Polymer A may be partially or totally neutralized by means of at least one monovalent ion or at least one divalent ion. According to the invention, polymer A may be partially or totally neutralized by means of a combination of at least one monovalent ion and at least one divalent ion. According to the invention, the total or partial neutralization of polymer A may then be achieved in varying relative molar proportions of the monovalent and divalent ions.Preferably according to the invention, the molar proportions of monovalent ion / divalent ion are between 90 / 10 and 10 / 90 or between 80 / 20 and 20 / 80, preferably between 80 / 20 and 60 / 40, for example 70 / 30 or 50 / 50.

[0023] According to the invention, neutralization can be achieved using a primary amine, a secondary amine, or a monovalent ion selected from K+, Na+, Li+, NH4+, and combinations thereof. The preferred ion is NH4+. According to the invention, neutralization can also be achieved using a divalent ion selected from Ca2+, Mg2+, and combinations thereof. The preferred divalent ion is Ca2+.

[0024] According to the invention, polymer A can be neutralized by means of at least one compound selected from NaOH, KOH, ammonium derivatives, ammonia, primary amine, secondary amine, CaO, Ca(OH)2, MgO, Mg(OH)2 and combinations thereof. According to the invention, polymer A can be neutralized totally or partially by means of an amino base, for example a base selected from ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, α,α'-diaminoxylene, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethanolamine, aminomethylpropanol or 2-amino-2-methylpropanol (AMP) and combinations thereof. Advantageously according to the invention, the amino base can also be present within composition R as an amino compound C.

[0025] Essentially, the composition R according to the invention comprises a compound B in an acidic form or in the form of a salt, preferably an ammonium salt. The compound B can be added to the polymer A and to the compound C during the preparation of the composition R. The compound B can also be obtained from the polymerization reaction of the monomer M in the presence of the sulfur compound T. When generated in situ, compound B is derived from the monomer M used. Preferably according to the invention, compound B is selected from sulfocarboxy-aromatic acids and sulfocarboxy-alkyl acids, preferably 3-sulfopropionic acid, 3-sulfo-2-methylpropionic acid, sulfosuccinic acid, their salts, and combinations thereof. The preferred compound B is 3-sulfopropionic acid. Preferred salts of compound B are selected from sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, and ammonium salt. The sodium or ammonium salt of compound B is particularly preferred.

[0026] Preferably according to the invention, composition R comprises a molar quantity of compound B greater than 5%, preferably greater than 10% or 15%, more preferably greater than 20% or 25%, relative to the molar quantity of sulfur IV. Also preferably according to the invention, the molar quantity of compound B in composition R is less than 60%, preferably less than 50% or 40%, relative to the molar quantity of sulfur IV. According to the invention, the molar quantity of compound B present in composition R relative to the molar quantity of sulfur IV is therefore generally within the ranges of 2% to 60% or 2% to 50% or 2% to 40%, preferably 5% to 60% or 5% to 50% or 5% to 40%.Also preferably, the molar quantity of compound B present in composition R relative to the molar quantity of sulfur IV is therefore generally within the ranges of 10% to 60% or 10% to 50% or 10% to 40%. Also preferably, the molar quantity of compound B present in composition R relative to the molar quantity of sulfur IV is within the ranges of 15% to 60% or 15% to 50% or 15% to 40% or even 25% to 60% or 25% to 50% or 25% to 40%.

[0027] Preferably, the composition R according to the invention comprises a monofunctional compound Cl. More preferably according to the invention, the compound Cl is a compound of formula I:

[0028] [Chem.I] T1- L*- T-

[0029] in which:

[0030] - T1 independently represents a C5-C32-aromatic group, a linear or branched C1-C32-alkyl group, - T2 independently represents OH or NH2, - L1 independently represents a group selected from (CH2-CH2O)X, (CH2CH(CH3)O)y, (CH(CH3)CH2O)z and their combinations and - x, y and z, whether identical or different, independently represent a number integer or decimal between 0 and 150, x is non-zero and the sum x+y+z is between 10 and 150 or x, y and z are zero.

[0031] Where appropriate, the combination of (CH2-CH2O)X groups and (CH2CH(CH3)O)y or (CH(CH3)CH2O)z groups is preferably defined by a molar ratio [x / (y+z)] ranging from 90 / 10 to 40 / 60 or from 60 / 40 to 50 / 50, for example 80 / 20 or 70 / 30.

[0032] More preferably, compound Cl is a compound of formula I in which T1 represents a methyl group. Also preferably, compound Cl is a compound of formula I in which T2 represents OH.

[0033] Also preferably, the compound Cl is a compound of formula I in which x is non-zero and L1 represents a (CH2-CH2O)X group.

[0034] Also preferably, the compound Cl is a compound of formula I in which x and y or z are non-zero and L1 represents a (CH2-CH2O)X group combined with a (CH2CH(CH3)O)y group or a (CH(CH3)CH2O)Z group.

[0035] An equally preferred compound Cl is a compound of formula I in which T1 represents a methyl group, T2 represents NH2 and L1 represents a (CH2-CH2O)x group and x represents a number from 10 to 150, preferably from 30 to 120.

[0036] An equally preferred compound Cl is a compound of formula I in which T1 represents a methyl group, T2 represents NH2, x and y or z are non-zero and L1 represents a (CH2-CH2O)X group combined with a (CH2CH(CH3)O)y group or a (CH(CH3)CH2O)Z group.

[0037] Also preferably, the compound Cia has a molecular mass ranging from 300 g / mol to 6,000 g / mol, preferably from 500 g / mol to 5,000 g / mol or from 1,000 g / mol to 3,000 g / mol.

[0038] Preferably, the composition R according to the invention comprises a polyfunctional compound C2. The compound C2 may be of synthetic or natural origin, for example, a monosaccharide or a glycoside. Monosaccharides (simple sugars) are selected from aldoses and ketoses. Glycosides are selected from holosides, in particular oligosaccharides, polysaccharides (for example, amylose, amylopectin, cellulose, glycogen), homopolysaccharides, heteropolysaccharides, or from heterosides, in particular O-heterosides, N-heterosides, and S-heterosides.

[0039] Preferably according to the invention, compound C2 is selected from glycerol, polyalkylene glycol (preferably polyethylene glycol, polypropylene glycol, polybutylene glycol), pentaerythritol, triethanolamine, ethanolamine, diethanolamine, 3-amino-l-propanol, l-amino-2-propanol, butanetriol, ethylene glycol, 1,3-propanediol, l,4-butanediol, l,6-hexanediol, pentaerythritol, sorbitol, 5-amino-l-pentanol, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, bis(N-hydroxyethyl)propane-1,3-diamine, diisopropanolamine, triisopropanolamine, N-methyldiethanolamine, N-butyldiethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, trimethylolpropane, trimethylolpropane 1,2,4 butanetriol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, D-arabinose, L-arabinose, D-xylose, D-glucose, D-mannose, D-gallactose, D-glucosamine, D-fructose, maltose, sucrose, lactose, ethyle-nediamine, diethylenetriamine, triethylenetetramine, 1,3-propanediamine, 1,2-propanediamine, neopentyldiamine, hexamethylenediamine, octamethyle-nediamine, N-(2-aminoethyl)propane-1,3-diamine, 1,2,3-propanetriamine, N,N-bis(3-aminopropylamine) et leurs combinaisons, de préférence choisi parmi glycerol, triethanolamine, trimethylolpropane 1,2,4, butanetriol,ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, sorbitol and their combinations. Also preferably, compound C2 has a molecular mass ranging from 50 to 1000 g / mol, preferably from 55 g / mol to 500 g / mol or from 55 g / mol to 250 g / mol.

[0040] Preferably according to the invention, composition R comprises a molar amount of compound C ranging from 5% to 100% relative to the total molar amount of carboxylic groups of polymer A. More preferably according to the invention, composition R comprises a molar amount of compound C ranging from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80% relative to the total molar amount of carboxylic groups of polymer A.

[0041] Advantageously, according to the invention, composition R comprises a molar amount of compound C ranging from 5% to 100% relative to the total molar amount of monomers. More advantageously, according to the invention, composition R comprises a molar amount of compound C ranging from 10% to 100%, or from 10% to 90%, or from 20% to 100%, or from 20% to 80% relative to the total molar amount of monomers.

[0042] The implementation of a compound Cl or C2 leads respectively to a composition RI which is prepared by means of a compound Cl or to a composition R2 prepared by means of a compound C2.

[0043] The composition R according to the invention may also comprise other compounds, in particular at least one compound selected from 2-sulfoacetic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, methanesulfonic acid, their salts and combinations thereof. The composition R may also comprise at least one compound selected from a compound comprising phosphorus in oxidation state I, a compound comprising phosphorus in oxidation state III, a compound comprising phosphorus in oxidation state V, and combinations thereof. Nevertheless Advantageously, the invention avoids the use of these phosphorus compounds. It can therefore be implemented in the absence of a compound containing phosphorus in oxidation state I, or in the absence of a compound containing phosphorus in oxidation state III, or in the absence of a compound containing phosphorus in oxidation state V. In such cases, composition R according to the invention does not contain any phosphorus compounds. The invention can also be implemented in the absence of a urea-formaldehyde compound or formaldehyde. In such cases, composition R according to the invention does not contain a urea-formaldehyde compound or formaldehyde.

[0044] The invention also provides a method for preparing an aqueous composition R according to the invention and which comprises:

[0045] • the preparation of an aqueous dispersion of polymer A according to the invention, • the retention, or possible addition, in the aqueous dispersion of polymer A of at least one compound B selected from a sulfocarboxylic acid, a salt of sulfocarboxylic acid and their combinations, • the addition of at least one compound C chosen from a monofunctional compound Cl chosen from monoalcohols and monoamines, a polyfunctional compound C2 chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), sugars and glycosides and combinations of compounds Cl and C2.

[0046] The composition R according to the invention can be used in various ways, in particular for the preparation of compounds resulting from the condensation, in the presence of compound B, of the carboxylic groups of polymer A with the hydroxylated groups or with the amine groups of compound C. Thus, the invention provides a method for preparing an ester compound or an amide compound comprising the preparation of a composition R according to the invention and then the reaction, by heating at a temperature above 100°C, of ​​the α-sulfonated polymer A and of compound C in the presence of compound B, preferably at a pH below 7, more preferably at a pH below 5.

[0047] Preferably, this preparation method according to the invention can be carried out with a compound Cl at a heating temperature ranging from 100 to 230°C or from 120 to 200°C. Preferably, this preparation method according to the invention can be carried out with a compound C2 at a heating temperature ranging from 100 to 280°C, preferably from 150 to 270°C or from 170 to 250°C, ranging from 100 to 250°C, preferably from 150 to 240°C or from 170 to 230°C.

[0048] The invention also relates to an ester compound prepared according to these methods. Preferably, this compound is a poly(carboxylate ether), a poly(amide ether), a crosslinked ester compound or a crosslinked amide compound, prepared according to any one of these methods. methods of the invention.

[0049] According to the invention, the particular, advantageous or preferred characteristics of the composition R according to the invention define methods for its preparation, methods for preparing an ester compound or an amide compound as well as these ester compounds or amide compounds which are also particular, advantageous or preferred.

[0050] The following examples illustrate the different aspects of the invention.

[0051] Preparation and characterization of polymers A according to the invention:

[0052] Preparation of the AA polymer according to the invention:

[0053] In a 1-liter glass reactor equipped with a stirrer, thermometer, and cooling system, a load consisting of 0.006 g of iron(II) sulfate heptahydrate and 380 g of water is prepared at room temperature. Then, three loads are prepared for parallel addition over a 3-hour period. The first beaker contains 623.5 g of acrylic acid, the second contains 5.086 g of sodium persulfate and 46.6 g of water, and the third contains 122.86 g of a 40 wt% aqueous sodium bisulfite solution. After 3 hours of addition at 73°C, a clear dispersion of polymer AA is obtained. The dry matter concentration is 55.2%. Polymer AA has a mass Mw of 4430 g / mol and an Ip of 2.2.

[0054] Preparation of polymer AB according to the invention:

[0055] In a 1-liter glass reactor equipped with a stirrer, thermometer, and cooling system, a load of 0.023 g of iron(II) sulfate heptahydrate and 284.13 g of water is prepared at room temperature. Then, three loads are prepared for parallel addition over a 3-hour period. First, a load of 0.74 g of sodium persulfate and 19.68 g of water is added to the reactor heated to 80°C. Next, 450.99 g of acrylic acid is added to a first beaker, 1.96 g of sodium persulfate and 19.68 g of water to a second beaker, and 94.23 g of a 40 wt. aqueous sodium bisulfite solution to a third beaker. After 3 hours of addition at 80°C, a clear dispersion of polymer AB is obtained. This polymer is then neutralized by adding sodium hydroxide until a pH of 2.0 is reached. The dry matter concentration is 50.0%. Polymer AB has a mass Mw of 6000 g / mol and an Ip of 2.7.

[0056] Preparation of the AC polymer according to the invention:

[0057] In a 1-liter glass reactor equipped with a stirrer, thermometer, and cooling system, a load of 0.023 g of iron(II) sulfate heptahydrate and 284.13 g of water is prepared at room temperature. Then, three loads are prepared and introduced in parallel over a 3-hour period. First, a load of 0.74 g of sodium persulfate and 19.68 g of water is introduced into the reactor heated to 80°C. Then, 450.99 g of acrylic acid is introduced into a first beaker, and into a second In a beaker, 1.96 g of sodium persulfate and 19.68 g of water were mixed, and in a third beaker, 94.23 g of a 40 wt% aqueous sodium bisulfite solution were mixed. After 3 hours of mixing at 80°C, a clear dispersion of polymer AC was obtained. The dry matter concentration was 48.3%. Polymer AC had a Mw of 6000 g / mol and an Ip of 2.7

[0058] Characterization of AA, AB and AC polymers according to the invention:

[0059] The compound B and the quantity of compound B (molar % relative to the molar quantity of sulfur IV of compound T implemented) included in each dispersion of polymer AA, AB and AC are determined by titration of sulfate ions and by 'H NMR and 13C NMR analysis of the sulfonated groups of polymer AA, AB or AC and of compound B.

[0060] The sulfate ion concentrations in polymer dispersions AA, AB, and AC are determined by ion chromatography. A sample of approximately 80 mg of the polymer dispersion is introduced into a 15 mL bottle. Mobile phase is added to a total mass of 15 g. The mobile phase composition is sodium carbonate: 0.009 mol / L. The ion chromatography system for anion determination consists of a Dionex Aquion ion chromatography system with an integrated degasser, set at a flow rate of 1 mL / min, containing a chemical suppressor, an AG9-HC pre-column, a CG3 metal-trapping pre-column, an NG1 pre-column, and an AG9-HC column. Detection is achieved using a conductivity detector. The ion chromatography system is calibrated with a series of sodium sulfate solution standards. The calibration range is between 0.5 and 100 ppm. The calibration curve is linear.Automatic sample dilution by the instrument ensures that the samples remain within the calibration range. Chromatogram acquisition and processing are performed using Chromeleon 7.2.10 software.

[0061] ¹H and ¹³C NMR analyses are performed using a Bruker AV III HD 500 spectrometer equipped with a 5 mm BBI probe. The polymer samples were dissolved in deuterated water and examined by ¹H and ¹³C NMR via 2D experiments: ¹H / ¹³C correlations at one distance and long distance.

[0062] The polymer dispersions AA, AB and AC according to the invention comprise 3-sulfopropionic acid as compound B. The results are presented in Table 1.

[0063] [Tables 1] Polymer AA AB AC Compound B (%) 15.0 38.8 38.8

[0064] Preparation and characterization of compositions R according to the invention:

[0065] Preparation and characterization of the RAI composition according to the invention:

[0066] In a 1-liter glass reactor equipped with a stirrer, thermometer, cooling system, and vacuum pump, a load is prepared at room temperature comprising 209.44 g of molten MPEG 2000 (methoxy polyethylene glycol with a molecular mass of 2000 g / mol), 1.01 g of Irganox 5057, 0.65 g of 50 wt% NaOH in water, and 80 g of AA polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. A temperature of 170°C is then maintained for 5 hours. The heating is then stopped. After cooling, the product is diluted to 50% in water. An esterified polymer is obtained having a mass Mw of 25,600 g / mol and an Ip of 1.7, the presence of ester functions of which is confirmed by the appearance of a peak at 1,700 cm⁻¹ in IR spectroscopy and by a peak at 4.2 ppm in ¹H NMR.

[0067] Preparation and characterization of the RB1 composition according to the invention:

[0068] In a 1-liter glass reactor equipped with a stirrer, thermometer, cooling system, and vacuum pump, a load is prepared at room temperature comprising 209.44 g of molten MPEG 2000 (methoxy polyethylene glycol with a molecular weight of 2000 g / mol), 1.01 g of Irganox 5057, 0.65 g of 50 wt% NaOH in water, and 89.21 g of AB polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. A temperature of 170°C is then maintained for 5 hours. Heating is then stopped. After cooling, the product is diluted to 50%. An esterified polymer is obtained having a mass Mw of 23,500 g / mol and an Ip of 1.6, the presence of ester functions of which is confirmed by the appearance of a peak at 1,700 cm1 in IR spectroscopy and by a peak at 4.2 ppm in H NMR.

[0069] Preparation and characterization of the RA2 composition according to the invention:

[0070] In a 1-liter glass reactor equipped with a stirrer, thermometer, cooling system, and vacuum pump, a load is prepared at room temperature comprising 164.41 g of TSPOE25 (25-fold tristyrylphenol ethoxylated with a molecular mass of 1570 g / mol), 1.01 g of Irganox 5057, 0.65 g of 50 wt% NaOH in water, and 80 g of AA polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. A temperature of 170°C is then maintained for 5 hours. Heating is then stopped. After cooling, the product is diluted to 50%. An esterified polymer is obtained having a mass Mw of 23,000 g / mol and an Ip of 1.7, the presence of ester functions of which is confirmed by the appearance of a peak at 1,700 cm1 in IR spectroscopy and by a peak at 4.2 ppm in H NMR.

[0071] Preparation and characterization of the RB2 composition according to the invention:

[0072] In a 1-liter glass reactor equipped with a stirrer, a thermometer, a cooling system, and a vacuum pump, a load is prepared at room temperature comprising 164.41 g of TSPOE25 (25-fold ethoxylated tristyrylphenol with a molecular mass of 1570 g / mol), 1.01 g of Irganox 5057, and 0.65 g of 50% NaOH. mass in water and 89.21 g of AB polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. Then, a temperature of 170°C is maintained for 5 h. The heating is stopped. After cooling, the product is diluted to 50%. An esterified polymer is obtained with a mass Mw of 21,300 g / mol and an Ip of 1.6, the presence of ester groups of which is confirmed by the appearance of a peak at 1,700 cm¹ by IR spectroscopy and by a peak at 4.2 ppm by ¹H NMR.

[0073] Preparation and characterization of the RA3 composition according to the invention:

[0074] In a 1-liter glass reactor equipped with a stirrer, thermometer, cooling system, and vacuum pump, a load is prepared at room temperature comprising 209.44 g of amine (co-methyl-α-amine ethoxylated 33.5 times, propoxylated 8.4 times, with a molecular mass of 2000 g / mol), 1.01 g of Irganox 5057, 0.65 g of 50 wt% NaOH in water, and 80 g of AA polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. A temperature of 170°C is then maintained for 5 hours. Heating is then stopped. After cooling, the product is diluted to 50%. We obtain an amidified polymer having a mass Mw of 34,000 g / mol and an Ip of 1.9 whose presence of amide functions is confirmed by the appearance of a peak at 3,200 cm⁻¹ in IR spectroscopy and by a peak at 3.3 ppm in ¹H NMR.

[0075] Preparation and characterization of the RB3 composition according to the invention:

[0076] In a 1-liter glass reactor equipped with a stirrer, thermometer, cooling system, and vacuum pump, a load is prepared at room temperature comprising 209.44 g of amine (co-methyl-α-amine ethoxylated 33.5 times, propoxylated 8.4 times, with a molecular mass of 2000 g / mol), 1.01 g of Irganox 5057, 0.65 g of 50 wt% NaOH in water, and 89.21 g of AB polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. A temperature of 170°C is then maintained for 5 hours. Heating is then stopped. After cooling, the product is diluted to 50%. An amidified polymer is obtained having a mass Mw of 33,000 g / mol and an Ip of 1.9, the presence of amide functions of which is confirmed by the appearance of a peak at 3,200 cm1 in IR spectroscopy and by a peak at 3.3 ppm in H NMR.

[0077] Preparation and characterization of composition RC1 according to the invention:

[0078] In a 1-liter glass reactor equipped with a stirrer, thermometer, cooling system, and vacuum pump, a load is prepared at room temperature comprising 209.44 g of molten MPEG 2000 (methoxy polyethylene glycol with a molecular mass of 2000 g / mol), 1.01 g of Irganox 5057, 0.65 g of 50 wt% NaOH in water, and 87.01 g of AC polymer dispersion. The reactor is heated to 100°C and subjected to a vacuum of 150 mbar. A temperature of 170°C is then maintained for 5 hours. Heating is then stopped. After cooling, the product is diluted. at 50%. We obtain an esterified polymer having a mass Mw of 23,300 g / mol and an Ip of 1.7 whose presence of ester functions is confirmed by the appearance of a peak at 1,700 cm1 in IR spectroscopy and by a peak at 4.2 ppm in H NMR.

[0079] Preparation of composition RA4 according to the invention:

[0080] 131.34 g of AA polymer dispersion comprising sulfopro- pionic (compound B) (mass concentration of dispersion: 55.2%) with 22.7 g of glycerol (polyfunctional compound C) and 24.2 g of water.

[0081] The dry extracts of composition RA4 and a glycerol sample are measured by heating at 110°C in an oven for 1 hour. The results (ESI - % by weight) are presented in Table 2.

[0082] Preparation of composition RB4 according to the invention:

[0083] 146.46 g of AB polymer dispersion comprising sulfopro- acid is mixed pionic (compound B) (mass concentration of dispersion: 49.5%) with 22.7 g of glycerol (polyfunctional compound C) and 24.2 g of water.

[0084] The dry extract of composition RB4 is measured by heating at 110°C in an oven for 1 hour. The result (DEI - % by weight) is presented in Table 2.

[0085] Characterization of compositions RA4 and RB4 according to the invention:

[0086] On a fiberglass substrate (Prat Dumas disc made of 100% borosilicate glass microfibers, 90 mm in diameter, 75 g / m², 480 µm thick), 1 g of composition RA4, or composition RB4 respectively, is applied. Each disc impregnated with the composition is placed in an oven and heated at 210°C for 5 minutes. After cooling, the dry extract is measured by heating the composite materials obtained by curing at 210°C in the oven for 1 hour at 110°C. The results (ES² - wt%) are presented in Table 2.

[0087] Then, in order to solubilize any remaining water-soluble substances, the composite materials are immersed in bi-permuted water for 1 hour at room temperature. After manual draining, the dry extracts of the composite materials are measured by heating them to 110°C in an oven for 1 hour. The results (ES3 - % by weight) are presented in Table 2. [Tables 2] ESI ES2 ES3 polymer dispersion AA 55.20 / / composition RA4 in composite 53.41 44.80 42.10 polymer dispersion AB 49.50 / / composition RB4 in composite 49.23 37.30 35.40

[0088] After crosslinking by heating at 210°C, the dry extracts ESI and ES2 of the com Positions RA4 and RB4 in the prepared composites confirm the condensation of the alcohol functions of glycerol and the carboxylic groups of polymers AA and AB. Furthermore, the dry extracts ES2 and ES3 confirm the formation of insoluble crosslinked composites.

Claims

Claims

1. Aqueous composition R comprising: a. at least one a-sulfonated polymer A prepared in water by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and combinations thereof, in the presence of at least one initiator compound and at least one sulfur compound T comprising sulfur in oxidation state IV, b. at least one compound B chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and combinations thereof, present in a molar quantity greater than 2% relative to the molar quantity of sulfur IV, c. at least one compound C selected from a monofunctional compound Cl selected from monoalcohols and monoamines, a polyfunctional compound C2 selected from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses and osides and combinations of compounds Cl and C2.

2. Composition R according to claim 1 for which: • polymer A is chosen from an a-co-disulfonated polymer Al, an a-monosulfonated polymer A2 and combinations thereof, or • polymer A has a weight-average molecular mass Mw (measured by CES) of less than 20,000 g / mol, preferably less than 15,000 g / mol, less than 10,000 g / mol, more preferably less than 7,000 g / mol or less than 6,000 g / mol, or • polymer A has a weight-average molecular mass Mw (measured by CES) greater than 1,000 g / mol or greater than 1,200 g / mol, or • polymer A has a polymolecularity index IP (measured by CES) less than 4 or ranging from 1.2 to 4 or from 1.5 to 4; from 1.2 to 3 or from 1.5 to 3; from 1.2 to 2.5 or even from 1.5 to 2.

5.

3. Composition R according to one of claims 1 or 2 for which: the monomer M is selected from acrylic acid, an acrylic acid salt and combinations thereof, or a combination of acrylic acid or an acrylic acid salt with methacrylic acid or with a methacrylic acid salt, or the monomer M is combined with at least one other monomer selected from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof, or the monomer M is selected from acrylic acid, an acrylic acid salt and combinations thereof, combined with at least one other monomer selected from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof, or the sulfur compound T is selected from lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, calcium di(hydrogen sulfite), magnesium di(hydrogen sulfite) and combinations thereof, or the polymerization reaction is carried out at a temperature above 30°C and below 100°C, preferably below 90°C, more preferably below 80°C or 75°C, or for which polymer A is prepared in the presence of at least one initiator compound chosen from a peroxide (for example hydrogen peroxide), a hydroperoxide (for example tert-butyl hydroperoxide), a persulfate (for example sodium persulfate, ammonium persulfate, potassium persulfate), their combinations and their associations with a metal salt, preferably a metal salt chosen from an iron salt (for example Fe II or Fe III), a copper salt (for example Cu I or Cu II) and their combinations, or • polymer A is non-neutralized or polymer A is partially or totally neutralized.

4. Composition R according to one of claims 1 to 3 for which: • the molar quantity of sulfur compound T, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of monomers used, • preferably the molar quantity of sulfur compound T, preferably the molar quantity of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar quantity of unsaturated groups of the monomers used.

5. Composition R according to one of claims 1 to 4 for which compound B is chosen from sulfo-carboxy-aromatic acids and sulfo-carboxy-alkyl acids, preferably 3-sulfopropionic acid, 3-sulfo-2-methyl-propionic acid, sulfo-succinic acid, and combinations thereof, or is a salt of compound B chosen from sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt and ammonium salt, preferably the sodium salt or the ammonium salt.

6. Composition R according to one of claims 1 to 5 comprising: • a molar quantity of compound B greater than 5%, preferably greater than 10% or 15%, more preferably greater than 20% or 25%, relative to the molar quantity of sulfur IV, or • a molar quantity of compound B less than 60%, preferably less than 50% or 40%, relative to the molar quantity of sulfur IV.

7. Composition R according to one of claims 1 to 6 for which: • the compound Cl is a compound of formula I: [Chem.l] T1- UP in which: - T1 independently represents a C5-C32-aromatic group, a linear or branched C1-C32-alkyl group, - T2 independently represents OH or NH2, - L1 independently represents a group chosen from (CH2-CH2O)x, (CH2CH(CH3)O)y, (CH(CH3)CH2O)Z and their combinations and - x, y and z, identical or different, independently represent an integer or decimal number between 0 and 150, x is non-zero and the sum x+y+z is between 10 and 150, or • the compound Cl has a molecular mass ranging from 300 to 6,000 g / mol, preferably from 500 to 5,000 g / mol or from 1,000 to 3,000 g / mol, or • compound C2 is chosen from glycerol polyalkylene glycol (preferably glycerol polyethylene glycol, polypropylene glycol, polybutylene glycol), pentaerythritol, triethanolamine and combinations thereof, or • compound C2 has a molecular mass ranging from 50 to 1000 g / mol, preferably from 55 to 500 g / mol or from 55 to 250 g / mol.

8. Composition R according to one of claims 1 to 7 for which • the molar quantity of compound C ranges from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80% relative to the total molar quantity of carboxylic groups of polymer A, or for which • the molar quantity of compound C ranges from 5% to 100%, preferably from 10% to 100% or from 10% to 90% or from 20% to 100% or from 20% to 80% relative to the total molar quantity of monomers.

9. Composition R according to one of claims 1 to 8 also comprising at least one compound chosen from 2-sulfoacetic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, their salts and their combinations.

10. Composition R according to one of claims 1 to 9 not comprising a urea-formaldehyde compound or formaldehyde or not comprising a compound comprising phosphorus in oxidation state I or not comprising a compound comprising phosphorus in oxidation state III or not comprising a compound comprising phosphorus in oxidation state V.

11. Composition R according to one of claims 1 to 9 chosen from a composition RI prepared using a compound Cl and a composition R2 prepared using a compound C2.

12. Method for preparing an aqueous composition R according to one of claims 1 to 11 comprising: • the preparation of a polymer A according to one of claims 1 to 6, • the maintenance, or the optional addition, in the aqueous dispersion of polymer A of at least one compound B chosen from a sulfocarboxylic acid, a sulfocarboxylic acid salt and their combinations and their salts • the addition of at least one compound C chosen from a monofunctional compound Cl chosen from monoalcohols and monoamines, a polyfunctional compound C2 chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses and osides and the combinations of compounds Cl and C2.

13. A method of preparing an ester or amide compound comprising preparing a composition R according to claim 12 and then reacting, by heating to a temperature above 100°C, the a-sulfonated polymer A and compound C in the presence of compound B, preferably at a pH below 7, more preferably at a pH below 5.

14. Preparation method according to claim 13 carried out with: • a compound Cl and at a heating temperature ranging from 100 to 230°C or from 120 to 200°C, or • a compound C2 and at a heating temperature ranging from 100 to 280°C, preferably from 150 to 270°C or from 170 to 250°C. ranging from 100 to 250°C, preferably from 150 to 240°C or from 170 to 230°C.

15. A compound prepared according to the method of one of claims 13 or 14, preferably poly(carboxylate ether), poly(amide ether), crosslinked ester compound or crosslinked amide compound, prepared according to the method of one of claims 13 or 14.