WO2023118675A1

WO2023118675A1 - Reactive polyacrylic composition

Info

Publication number: WO2023118675A1
Application number: PCT/FR2022/000139
Authority: WO
Inventors: Jean-Marc Suau; Ludovic BALMEFREZOL; Laurie PARRENIN
Original assignee: Coatex
Priority date: 2021-12-20
Filing date: 2022-12-19
Publication date: 2023-06-29
Also published as: FR3130808A1

Abstract

The invention relates to a composition for preparing a (poly)ester compound or a (poly)amide compound. Said 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

REACTIVE POLYACRYLIC COMPOSITION

The invention relates to a composition for preparing a (poly)ester compound or a (poly)amide compound. This composition comprises an a-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 by means of this composition.

Many technical fields use 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 amino group. They can also be prepared from polyfunctional compounds comprising at least two hydroxyl or amine groups.

Typically, ester or amide formation is achieved in a heated and catalyzed reaction. Known effective catalysts include phosphorus, especially phosphorus in oxidation state I, III or V. Reducing or eliminating a phosphorus catalyst could be compensated by increasing the temperature of the reaction. However, such an increase in temperature can lead to a strong degradation of the efficiency of the formation of an ester or an amide. A high temperature can lead to the decarboxylation of the (meth)acrylic polymer or even to the degradation of the reactants and the reaction products. The formation of degradation by-products or colored by-products, in particular due to excessive exposure to high temperatures, must be reduced or avoided.

Ester or amide forming compositions, especially crosslinkable compositions, should possess high reactivity. They should allow high reaction kinetics. Indeed, it is always useful to better control the reaction kinetics of ester or amide formation.

Furthermore, the esters or the amides should be able to be prepared in the absence of a compound which may be considered harmful from an environmental point of view or else in the absence of a compound whose use is restricted by regulatory provisions. In particular, the preparation of these compounds in the absence of a compound comprising phosphorus should be preferred, in particular the absence of phosphorus in oxidation state I, III or V.

Ester or amide compounds can have many particularly advantageous properties in their fields of use. However, these properties can be improved or degraded depending on the conditions under which the ester or amide compounds are prepared.

Poly(ester) or poly(amide) compounds can be used in fields requiring structuring properties or insulating properties. In particular, these crosslinkable polymers can be applied to a material in the form of fibers or particles, in particular glass or rock, or else fibers of organic material, for example organic optical fibers. These polymers can also be used to produce coatings, in particular water-repellent coatings or mechanical, physico-chemical or chemical protective coatings.

Poly(ester) or poly(amide) compounds can also be used in fields requiring properties for dispersing hydrophobic organic substances or for dispersing solid and water-insoluble mineral substances.

The 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 make it possible to fix the carbon or metal particles on a metallic substrate. The binding power is therefore decisive when manufacturing an anode using these anode compositions.

Document US 20030050404 describes the preparation of poly(meth)acrylic acid in the presence of sulfur IV then the modification of this polyacid with an amino-PEG in the presence of sulfuric acid. Document US 20090240023 describes the preparation of a crosslinked and esterified acrylic copolymer by means of a mixture of a short-chain alcohol and a long-chain alcohol and in the presence of para-toluene sulphonic acid. Document WO 2016092190A1 describes the preparation of a comb polymer by esterification or amidification of an acid polymer by hot reaction in a tubular reactor. Document WO 2019234313 describes a method for treating sludge from metallic ore by means of a polymer of acrylic acid prepared in the presence of persulfate and sodium bisulfite or sodium hypophosphite. Document CN 104945634 discloses a water-reducing compound for a cement or concrete composition which is prepared from a copolymer prepared in the presence of sodium bisulphite.

The ester preparation or aid compositions of the state of the art do not always make it possible to provide satisfactory solutions. There is therefore a need for improved compositions for the preparation of a compound (poly jester or for the preparation of a compound (poly) amide. The invention makes it possible to provide a solution to all or part of the problems of the compositions for preparing a compound (poly jester or for preparing a compound (polyamide of the state of the art.

The invention provides an aqueous composition R comprising: a) at least one a-sulphonated polymer A prepared in water by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, an acid salt acrylic acid, 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 sulfo-carboxylic acid, a sulfo-carboxylic acid salt and combinations thereof, present in a molar amount measured according to the method of the description, greater than 2% relative to the molar amount of sulfur IV, c) 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, (polyaminojalcools, amino (polyalcohols), oses and osides and combinations of compounds Cl and C2.

Essentially according to the invention, polymer A is an α-sulfonated polymer. It therefore comprises a sulfonated group in the terminal position. Preferably according to the invention, the polymer A is chosen from an a-co-disulphonated polymer A1, an a-monosulphonated polymer A2 and their combinations. Polymer Al therefore comprises a single sulphonated group on one of its terminal positions, while polymer A2 comprises a sulphonated group on each of its two terminal positions. 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 well a combination of acrylic acid or a salt of acrylic acid with methacrylic acid or with a salt of methacrylic acid.

According to the invention, the monomer M can be combined with at least one other monomer, preferably another monomer chosen from vinyl acetate, ethyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-acrylamido acid -2-methylpropane sulfonic (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof. In combination with another monomer, the monomer M can be chosen from acrylic acid, an acrylic acid salt and combinations thereof, in combination with at least one other monomer chosen from vinyl acetate, ethyl acrylate, methyl, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid 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, the monomer M is acrylic acid alone.

Preferably according to the invention, the polymer A is not crosslinked or else it is prepared in the absence of diacrylate derivative, in particular in the absence of dipropylene glycol diacrylate and of tripropylene glycol diacrylate.

Essentially, polymer A is prepared during a polymerization reaction of monomer M in the presence of a sulfur compound T comprising sulfur IV. Preferably, the sulfur compound T is chosen from lithium hydrogen sulphite, sodium hydrogen sulphite, potassium hydrogen sulphite, ammonium hydrogen sulphite, calcium di(hydrogen sulphite), magnesium di(hydrogen sulphite) and combinations thereof. Preferably according to the invention, the compound T is a mono-hydrogen sulphite. The preferred sulfur compound T is sodium hydrogen sulphite, also called sodium bisulphite. Preferably according to the invention, the molar amount of sulfur compound T, preferably the molar amount of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the amount total molar of monomers used. More preferably, the molar amount of sulfur compound, preferably the molar amount of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar amount of groups unsaturated monomers used.

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, during the polymerization reaction, the initiator compound is chosen from a peroxide (for example hydrogen peroxide), a hydroperoxide (for example /erZ-butyl hydroperoxide), a persulfate (for example sodium persulfate, persulfate ammonium, 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.

Preferably, 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 6000 g/mol. Polymer A generally has a weight-average molecular mass Mw (measured by CES) greater than 1000 g/mol or greater than 1200 g/mol.

Preferably, polymer A has a polydispersity 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.

According to the invention, the weight or molecular mass of the polymer A is determined by Steric Exclusion Chromatography (CES) or in English “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 to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCOs: 0.05 mol/L, NaNOs: 0.1 mol/L, triethanolamine: 0.02 mol/L, NaNs 0.03% by mass. The CES chain is made up of a Waters 510 type isocratic pump, the flow rate of which is set at 0.8 mL/min, a Waters 717+ sample changer, an oven containing a Guard type precolumn Column Ultrahydrogel Waters 6 cm long and 40 mm inside diameter, followed by a linear column of Ultrahydrogel Waters type 30 cm long and 7.8 mm inside diameter. Detection is ensured by means of a differential refractometer of the RI Waters 410 type. The oven is brought to a temperature of 60° C. and the refractometer is brought to a temperature of 45° C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standard Service with a peak apex molecular weight between 900 and 2,250,000 g/mol and a polydispersity index between 1.4 and 1 ,7. The calibration curve is linear and takes into account the correction obtained using the flow marker: dimethylformamide (DMF). The acquisition and processing of the chromatogram are carried out using the PSS WinGPC Scientific v 4.02 software. The chromatogram obtained is integrated in the zone corresponding to molecular weights greater than 250 g/mol.

According to the invention, the polymer A can be non-neutralized or it can be partially neutralized or completely neutralized. Preferably, polymer A is non-neutralized. According to the invention, the carboxylic groups of polymer A can be partially neutralized at a rate of 70 to 97% molar, preferably at a rate of 90 to 95% molar. Polymer A can be partially or totally neutralized by means of at least one monovalent ion or at least one divalent ion. According to the invention, the polymer A can 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 the polymer A can then be carried out in variable relative molar proportions of the monovalent and divalent ions. Preferably, according to the invention, the monovalent ion/divalent ion molar proportions 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.

According to the invention, the neutralization can be carried out by means of a primary amine, a secondary amine or a monovalent ion chosen from K ⁺ , Na ⁺ , Li ⁺ , NH4 ⁺ and their combinations. The preferred ion is NH4 ⁺ . According to the invention, the neutralization can also be carried out by means of a divalent ion chosen from Ca ²⁺ , Mg ²⁺ , Zn ²⁺ and their combinations. The preferred divalent ion is Ca ²⁺ .

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

Essentially, the composition R according to the invention comprises a compound B in an acid form or else in the form of a salt, preferably an ammonium salt. Compound B can be added to polymer A and to compound C during the preparation of composition R. Compound B can also result from the polymerization reaction of monomer M in the presence of sulfur compound T. When it is generated in in situ, compound B is then derived from the monomer M used. Preferably according to the invention, 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, their salts and their combinations. The preferred compound B is 3-sulfopropionic acid. The preferred salts of compound B are chosen from sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt and ammonium salt. The sodium salt or the ammonium salt of compound B are particularly preferred.

According to the invention, compound B and the quantity of compound B (% molar relative to the molar quantity of sulfur IV of the compound T used) are determined by assaying the sulphate ions and by 'H NMR and ¹³ C NMR analysis. sulphonated groups of polymer A and of compound B.

Preferably according to the invention, composition R comprises a molar quantity of compound B greater than 5%, preferably greater than 10% or 15%, plus 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 within 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 amount of compound B present in composition R relative to the molar amount 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 amount of compound B present in composition R relative to the molar amount 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 amount of compound B present in composition R relative to the molar amount of sulfur IV is within the ranges of 15% to 60% or 15% to 50% or 15% to 40% or even from 25% to 60% or from 25% to 50% or from 25% to 40% or even from 20% to 60% or from 20% to 50% or from 20% to 40%.

Preferably according to the invention, the composition R comprises at least one compound C chosen from a monofunctional compound C1 and a polyfunctional compound C2. Preferably according to the invention, the composition R comprises a single compound C or else a single compound Cl combined with at least one compound C2 or else a single compound C2 combined with at least one compound Cl.

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

T ¹ - L'-T-' _(I) in which:

T ¹ independently represents a C5-C32-aromatic group, a linear or branched Ci-C32-alkyl group,

T ² independently represents OH or NH2,

L ¹ independently represents a group chosen from (CH2-CH2O) _X , (CH ₂ CH(CH ₃ )O) _y , (CH(CH ₃ )CH ₂ O) _Z and their combinations and x, y and z, which are identical or different, independently represent an integer or decimal between 0 and 150, x is non-zero and the sum x+y+z is between 10 and 150 or else x, y and z are zero.

Where appropriate, the combination of groups (CEh-CEhO and groups (CH2CH(CH3)O) _y or (CH(CH3)CH2O) _Z 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 More preferably, compound C1 is a compound of formula I in which T ¹ represents a methyl group. Also preferably, compound Cl is a compound of formula I in which T ² represents OH.

Also preferably, compound Cl is a compound of formula I in which x is non-zero and L ¹ represents a (CH2-CH2O) _X group.

Also preferably, compound Cl is a compound of formula I in which x and y or z are non-zero and L ¹ represents a (CH2-CH2O) _X group combined with a (CH2CH(CH3)O) _y group or a (CH(CH3)CH2O) _Z group.

A compound C 1 which is also preferred is a compound of formula I in which T ¹ represents a methyl group, T ² represents NH2 and L ¹ represents a group (CH2-CH2O) _X and x represents a number ranging from 10 to 150, preferably ranging from 30 to 120.

A compound C 1 which is also preferred is a compound of formula I in which T ¹ represents a methyl group, T ² represents NH2, x and y or z are non-zero and L ¹ represents a group (CH2-CH2O) _X combined with a group (CH2CH(CH3)O) _y or a (CH(CH ₃ )CH ₂ O)Z group.

Also preferably, compound C1 has a molecular mass ranging from 300 g/mol to 6000 g/mol, preferably from 500 g/mol to 5000 g/mol or from 1000 g/mol to 3000 g/mol. soft.

Also very preferably, the composition R according to the invention comprises a polyfunctional compound C2. Compound C2 can be of synthetic origin or of natural origin, for example an ose or an oside. The oses (simple sugars) are chosen from aldoses and ketoses. The osides are chosen from holosides, in particular from oligoholosides, polyholosides (for example amylose, amylopectin, cellulose, glycogen), homopolyosides, heteropolyosides or else among the heterosides, in particular among the O-heterosides, the N-heterosides, the S-heterosides.

Preferably according to the invention, compound C2 is chosen from glycerol, polyalkylene glycol (preferably polyethylene glycol, polypropylene glycol, polybutylene glycol), pentaerythrytol, triethanolamine, ethanolamine, diethanolamine, 3-amino-1-propanol, l-amino-2-propanol , butanetriol, ethylene glycol, 1,3 -propanediol, 1,4- butanediol, 1,6-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, ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propanediamine, 1,2-propanediamine, neopentyldiamine, hexamethylenediamine, octamethylenediamine, N-(2-aminoethyl)propane- 1 ,3-diamine, 1,2,3 -propanetriamine, N,N-bis(3-aminopropylamine) and combinations thereof, preferably chosen from glycerol, triethanolamine, 1,2,4-trimethylolpropane, butanetriol, ethyleneglycol, 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.

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.

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 amount total molar of monomers.

The implementation of a compound C1 or C2 leads respectively to a composition R1 which is prepared by means of a compound C1 or to a composition R2 prepared by means of a compound C2.

Composition R according to the invention may also comprise other compounds, in particular at least one compound chosen from 2-sulfoacetic acid, para-toluenesulfonic acid (PTSA), sulfuric acid, methanesulfonic acid, their salts and their combinations, preferably chosen from 2-sulphoacetic acid, para-toluene sulphonic acid (PTSA), their salts and their combinations, more preferably from 2-sulphoacetic acid and its salts. Advantageously, composition R according to the invention does not comprise sulfuric acid or para-toluenesulfonic acid. Composition R may also comprise at least one compound chosen 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 and advantageously, the invention makes it possible to avoid the use of these phosphorus compounds. It can therefore be implemented in the absence of a compound comprising phosphorus in the degree of oxidation I or in the absence of a compound comprising phosphorus in the degree of oxidation III or in the absence of a compound comprising phosphorus in the degree oxidation V. Then, the composition R according to the invention does not comprise any phosphorus compound. The invention can also be implemented in the absence of urea-formaldehyde compound or formaldehyde. Then, the composition R according to the invention does not comprise a urea-formaldehyde compound or formaldehyde.

The invention also provides a method for preparing an aqueous composition R according to the invention and which comprises: the preparation of an aqueous dispersion of polymer A according to the invention, maintaining, or optionally adding, in the dispersion aqueous polymer A of at least one compound B chosen from a sulpho-carboxylic acid, a sulpho-carboxylic acid salt and combinations thereof, 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 C1 and C2.

Composition R according to the invention can be used in different 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 hydroxyl groups or with the amino 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 then the reaction, by heating to a temperature above 100° C., of the polymer A a-sulfonated and compound C in the presence of compound B, preferably at a pH below 7, more preferably at a pH below 5.

Also preferably, this method of preparation according to the invention can be implemented with a compound C1 at a heating temperature ranging from 100 to 230°C or from 120 to 200°C. Preferably, this method of preparation according to the invention can be implemented 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.

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 one or other of the methods of the invention.

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 compound or amide compound which are also particular, advantageous or preferred. The following examples illustrate the various aspects of the invention.

Preparation and characterization of polymers A according to the invention:

Preparation of the AA polymer according to the invention: In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system, a charge comprising 0.006 g of iron sulphate heptahydrate and 380 g of water is prepared at room temperature. Then, 3 charges are prepared to be introduced in parallel for 3 hours. 623.5 g of acrylic acid are introduced into a first beaker, 5.086 g of sodium persulfate and 46.6 g of water into a second beaker and 122.86 g of an aqueous solution of sodium persulfite into a third beaker. sodium at 40% by weight. After 3 hours of addition at 73° C., a clear dispersion of AA polymer 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.

Preparation of the AB polymer according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system, a charge comprising 0.023 g of iron sulphate heptahydrate and 284.13 g of water is prepared at room temperature. Then, 3 charges are prepared to be introduced in parallel for 3 hours. A charge of 0.74 g of sodium persulfate and 19.68 g of water is first introduced into the reactor heated to 80° C. Then, 450.99 g of acrylic acid are introduced into a first beaker, into a second beaker 1.96 g of sodium persulfate and 19.68 g of water and into a third beaker 94.23 g of a solution aqueous sodium bisulphite at 40% by weight. 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 to a pH of 2.0. The dry matter concentration is 50.0%. Polymer AB has a mass Mw of 6000 g/mol and an Ip of 2.7.

Preparation of the AC polymer according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system, a charge comprising 0.023 g of iron sulphate heptahydrate and 284.13 g of water is prepared at room temperature. Then, 3 charges are prepared to be introduced in parallel for 3 hours. First of all, a charge 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 are introduced into a first beaker, into a second beaker 1.96 g of sodium persulfate and 19.68 g of water and into a third beaker 94.23 g of a solution aqueous sodium bisulphite at 40% by weight. After addition for 3 hours at 80° C., a clear dispersion of AC polymer is obtained. The dry matter concentration is 48.3%. Polymer AC has a Mw of 6000 g/mol and an Ip of 2.7. Characterization of the AA, AB and AC polymers according to the invention:

Compound B and the amount of compound B (molar % relative to the molar amount of sulfur IV of compound T used) included in each dispersion of polymer AA, AB and AC are determined by assaying sulfate ions and by NMR analysis 'H and ¹³ C NMR of the sulphonated groups of the polymer AA, AB or AC and of the compound B.

The sulfate ion levels in the polymer dispersions AA, AB and AC are determined by ion chromatography. A test portion of the polymer dispersion of approximately 80 mg is introduced into a 15 mL bottle. Mobile phase is added, up to a total mass of 15 g. The composition of the mobile phase is as follows: sodium carbonate: 0.009 mol/L. The ion chromatography chain for anion dosage is made up of a Dionex Aquion type ion chromatography system with integrated degasser, the flow rate of which is set at 1 mL/min, containing a chemical suppressor, an AG9-HC precolumn, a precolumn CG3 metal trap, an NG1 guard column and an AG9-HC column. Detection is ensured by means of a conductometric detector. The ion chromatography device is calibrated with a standard series of sodium sulfate solutions. The calibration range is between 0.5 and 100 ppm. The calibration curve is linear. An automatic dilution of the samples by the device makes it possible to be in the calibration range. The acquisition and processing of the chromatogram are carried out using the Chromeleon 7.2.10 software.

The ^X H NMR and ¹³ C NMR analyzes are carried out 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 1 H NMR and ¹³ C NMR via the 2D experiments: single-range and long-range 1 H / ¹³ C correlations.

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.

Table 1

Preparation and characterization of compositions R according to the invention:

Preparation and characterization of the RAI composition according to the invention: In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge 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 NaOH at 50% by weight in water and 80 g of polymer dispersion AA. The reactor is heated to 100° C. and subjected to a vacuum of 150 mbar. Then, a temperature of 170° C. is imposed for 5 h. The heating is stopped. After cooling, the product is diluted to 50% in water. An esterified polymer having a mass Mw of 25,600 g/mol and an Ip of 1.7 is obtained, the presence of the 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 ^X H NMR.

Preparation and characterization of the RB1 composition according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge 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 NaOH at 50% by weight in water and 89.21 g of polymer dispersion AB. The reactor is heated to 100° C. and subjected to a vacuum of 150 mbar. Then, a temperature of 170° C. is imposed for 5 h. The heating is stopped. After cooling, the product is diluted to 50%. An esterified polymer having a mass Mw of 23,500 g/mol and an Ip of 1.6 is obtained, the presence of the 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 ^X H NMR.

Preparation and characterization of the RA2 composition according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge comprising 164.41 g of TSPOE25 (tristyryl phenol ethoxylated 25 times with a molecular mass of 1570 g/mol), 1.01 g of Irganox 5057, 0.65 g of NaOH at 50% by weight in water and 80 g of polymer dispersion AA. The reactor is heated to 100° C. and subjected to a vacuum of 150 mbar. Then, a temperature of 170° C. is imposed for 5 h. The heating is stopped. After cooling, the product is diluted to 50%. An esterified polymer having a mass Mw of 23,000 g/mol and an Ip of 1.7 is obtained, the presence of the 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 ^X H NMR. Preparation and characterization of the RB2 composition according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge comprising 164.41 g of TSPOE25 (tristyryl phenol ethoxylated 25 times with a molecular weight of 1570 g/mol), 1.01 g of Irganox 5057, 0.65 g of NaOH at 50% by mass in water and 89.21 g of polymer dispersion AB. The reactor is heated to 100° C. and subjected to a vacuum of 150 mbar. Then, a temperature of 170° C. is imposed for 5 h. The heating is stopped. After cooling, the product is diluted to 50%. An esterified polymer having a mass Mw of 21,300 g/mol and an Ip of 1.6 is obtained, the presence of the 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 ^X H NMR.

Preparation and characterization of the RA3 composition according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge comprising 209.44 g of amine (co -methyl-a-amine ethoxylated 33.5 times, propoxylated 8.4 times, molecular weight 2,000 g/mol), 1.01 g of Irganox 5057, 0.65 g of NaOH at 50% by mass in water and 80 g of AA polymer dispersion. The reactor is heated to 100° C. and subjected to a vacuum of 150 mbar. Then, a temperature of 170° C. is imposed for 5 h. The heating is stopped. After cooling, the product is diluted to 50%. An amidated polymer having a mass Mw of 34,000 g/mol and an Ip of 1.9 is obtained, the presence of the amide functions of which 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 ^X H NMR.

Preparation and characterization of the RB 3 composition according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge comprising 209.44 g of amine (co -methyl-a-amine ethoxylated 33.5 times, propoxylated 8.4 times, molecular weight 2,000 g/mol), 1.01 g of Irganox 5057, 0.65 g of NaOH at 50% by 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 imposed for 5 h. The heating is stopped. After cooling, the product is diluted to 50%. An amidated polymer having a mass Mw of 33,000 g/mol and an Ip of 1.9 is obtained. 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 ¹ H NMR.

Preparation and characterization of the RC1 composition according to the invention:

In a 1 liter glass reactor equipped with stirring, a thermometer and a cooling system and a vacuum pump, a charge 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 NaOH at 50% by weight in water and 87.01 g of polymer dispersion AC. The reactor is heated to 100° C. and subjected to a vacuum of 150 mbar. Then, a temperature of 170°C is imposed for 5 hours. The heating is stopped. After cooling, the product is diluted to 50%. An esterified polymer having a mass Mw of 23,300 g/mol and an Ip of 1.7 is obtained, the presence of the 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 ¹ H NMR.

Preparation of composition R A4 according to the invention:

131.34 g of dispersion of AA polymer comprising sulfopropionic acid (compound B) (mass concentration of the dispersion: 55.2%) are mixed with 22.7 g of glycerol (polyfunctional compound C) and 24.2 g of water.

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

Preparation of the RB4 composition according to the invention:

146.46 g of polymer dispersion AB comprising sulfopropionic acid (compound B) (mass concentration of the dispersion: 49.5%) are mixed with 22.7 g of glycerol (polyfunctional compound C) and 24.2 g of water.

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

Characterization of the RA4 and RB4 compositions according to the invention:

On a fiberglass substrate (Prat Dumas disk of 100% borosilicate glass microfibers, 90 mm in diameter, weight 75 g/m ² , thickness 480 μm), 1 g of composition RA4, respectively of composition RB4. Each disc impregnated with composition is placed in an oven and heated to 210° C. for 5 minutes. After cooling, the dry extract is measured by heating at 110° C. in an oven for 1 hour of the composite materials obtained by baking at 210° C. The results (ES2-% by weight) are presented in Table 2. Then, in order to solubilize the water-soluble substances still present, the composite materials are immersed in bipermuted water for 1 hour at room temperature. After manual draining, the dry extracts of the composite materials are measured by heating at 110° C. in an oven for 1 hour. The results (ES3 - % by weight) are shown in Table 2.

Table 2

After crosslinking by heating to 210° C., the dry extracts ESI and ES2 of the compositions RA4 and RB4 in the composites prepared confirm the condensation of the alcohol functions of the glycerol and of the carboxylic groups of the polymers AA and AB. In addition, the dry extracts ES2 and ES3 clearly confirm the formation of insoluble crosslinked composites.

Claims

CLAIMS Aqueous composition R comprising: a) at least one a-sulphonated polymer A prepared in water by a polymerization reaction of at least one monomer M chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a 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 chosen from a sulfo-carboxylic acid , a sulpho-carboxylic acid salt and combinations thereof, present in a molar amount, measured according to the method of the description, greater than 2% relative to the molar amount of sulfur IV, c) at least one compound C chosen from a monofunctional compound C1 chosen from monoalcohols and monoamines, a polyfunctional compound C2 chosen from polyols, polyamines, aminoalcohols, (polyamino)alcohols, amino(polyalcohols), oses and osides and combinations of compounds C1 and C2. Composition R according to Claim 1, in which: polymer A is chosen from an a-co-disulphonated polymer Al, an a-monosulphonated polymer A2 and combinations thereof, or polymer A has a weight-average molecular mass Mw (measured by CES ) 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 polydispersity index IP (measured by CES) less than 4 or ranging from 1, 2 to 4 or 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. Composition R according to one of Claims 1 or 2, in which: the monomer M is chosen from acrylic acid, a salt of acrylic acid and combinations thereof, or else a combination of acrylic acid or of a salt of acrylic acid with methacrylic acid or with a salt of methacrylic acid, or the monomer M is combined with at least one other monomer chosen 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, or the monomer M is chosen from acrylic acid, a salt of acrylic acid and combinations thereof, combined with at least one other monomer chosen from vinyl acetate, ethyl acrylate, acrylate of methyl, hydroxy ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), maleic acid, maleic anhydride, itaconic acid and combinations thereof, or the sulfur compound T is chosen from lithium hydrogen sulphite, hydrogen sulphite sodium sulphite, potassium hydrogen sulphite, ammonium hydrogen sulphite, calcium di(hydrogen sulphite), magnesium di(hydrogen sulphite) and combinations thereof, or the polymerization reaction is carried out at a temperature above 30°C and below 100° C, preferably less than 90° C., more preferably less than 80° C. or 75° C., or for which the polymer A is prepared in the presence of at least one initiator compound chosen from a peroxide (for example peroxide of hydrogen), a hydroperoxide (for example /erZ-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 combinations thereof, or polymer A is non-neutralized or polymer A is partially or totally neutralized , or polymer A is not crosslinked or else polymer A is prepared in the absence of diacrylate derivative, in particular in the absence of dipropylene glycol diacrylate and of tripropylene glycol diacrylate. Composition R according to one of Claims 1 to 3 for which: the molar amount of sulfur compound T, preferably the molar amount of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar amount of monomers used, preferably the molar amount of sulfur compound T, preferably the molar amount of sulfur IV, is between 1% and 15%, preferably between 1.5% and 12%, relative to the total molar amount of unsaturated groups of 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, acid 3 -sulfo-2-methyl-propionic, sulfo-succinic acid, and combinations thereof, or is a salt of compound B selected from sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt and ammonium salt, preferably sodium salt or ammonium salt.

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

T'- L'-T ² (J) in which:

- T ¹ independently represents a C5-C32-aromatic group, a linear or branched Ci-C32-alkyl group,

- T ² independently represents OH or NH2,

- L ¹ independently represents a group chosen from (CH2-CH2O) _X , (CH ₂ CH(CH ₃ )O) _y , (CH(CH ₃ )CH ₂ O) _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 22

• compound Cl has a molecular mass ranging from 300 to 6000 g/mol, preferably from 500 to 5000 g/mol or from 1000 to 3000 g/mol, or

• compound C2 is chosen from glycerol polyalkylene glycol (preferably glycerol polyethylene glycol, polypropylene glycol, polybutylene glycol), pentaerythrytol, triethanolamine and their combinations, 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, of preferably chosen from 2-sulphoacetic acid, para-toluene sulphonic acid (PTSA), their salts and combinations thereof, more preferably 2-sulphoacetic acid and its salts.

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 the degree of oxidation I or not comprising a compound comprising phosphorus in the degree 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 R1 prepared using a compound C1 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: 23 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 sulfo-carboxylic acid, a sulfo-carboxylic 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, amino alcohols, (polyamino ) alcohols, amino (polyalcohols), oses and osides and combinations of compounds C1 and C2.

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

14. Method of preparation according to claim 13 implemented with: a compound C 1 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 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. 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 .