Thickener for hydroalcoholic compositions

Abstract

This invention relates to a thickener P for use in aqueous compositions, particularly for hydroalcoholic compositions. The thickener P is prepared in the absence of acrylamide by polymerization of N-hydroxymethylacrylamide or its derivatives, acids, and esters. Specific condensates of (meth)acrylic acid and N-hydroxymethylacrylamide are part of this invention. The invention also provides hydroalcoholic compositions with controlled viscosity.

Description

[0001] This invention relates to a thickener P for use in aqueous compositions, particularly for hydroalcoholic compositions. The thickener P is prepared in the absence of acrylamide by polymerization of N-hydroxymethylacrylamide or its derivatives, acids, and esters. Specific condensates of (meth)acrylic acid and N-hydroxymethylacrylamide are part of this invention. This invention also provides hydroalcoholic compositions having controlled viscosity.

[0002] When using aqueous compositions, the appearance and form of the composition are its fundamental properties. In particular, for ease of use and to improve its effectiveness, aqueous compositions must have a controlled viscosity. Especially, hydroalcoholic compositions must have a viscosity suitable for their use.

[0003] When using water-alcohol compositions, it is important to avoid splashing or loss of the composition. It is equally important to be able to apply it easily without loss or difficulty.

[0004] Furthermore, the compatibility between the various components of the hydroalcohol composition is also a very important property. It is particularly important that the hydroalcohol composition contains a high proportion of at least one alcohol, especially a high proportion of ethanol or isopropanol.

[0005] Controlling viscosity is often difficult when preparing stable aqueous-alcohol compositions for several reasons. In fact, adding alcohol to an aqueous composition tends to significantly reduce surface tension, making it difficult to maintain viscosity. Furthermore, adding alcohol to such an aqueous composition may increase the solubility of other components, thereby compromising the stability of the aqueous-alcohol composition.

[0006] Thickeners used in aqueous compositions, especially hydroalcoholic compositions, are not always effective enough to address the various problems encountered.

[0007] Document WO2006016035 discloses a hydroalcoholic composition containing a hydrophobic thickening compound. Document JP2019003926 discloses a thickening compound for electrode preparation suspensions. Document JPS4828555 discloses an unsaturated compound. Document GB1356030 discloses an adhesive compound for coated paper. Document DE2531235 discloses a thickening compound for paint or printing pulp.

[0008] In addition, some known thickeners are prepared from acrylamide (H₂C=C(=O)OCH₂NH₂). Since this compound is often considered problematic or even to be avoided, it is important to be able to prepare thickeners in the absence of acrylamide.

[0009] The form of the thickener used in aqueous compositions, particularly hydroalcoholic compositions, is also important. Therefore, it is particularly advantageous for the thickener to be in the form of an aqueous dispersion or solid that can be readily incorporated into such compositions. Using a powdered thickener, in particular, avoids the use of organic solvents other than alcohols. In aqueous compositions, especially hydroalcoholic compositions, avoiding the use of any organic solvents other than alcohols can potentially limit or eliminate problems associated with these solvents, particularly those related to their handling or regulatory or health issues related to their presence.

[0010] The preparation of hydroalcoholic compositions can also present problems. For example, thorough and uniform blending of the various components is crucial. Stability, including viscosity retention, is also an important property of thickened aqueous compositions, especially for thickened hydroalcoholic compositions.

[0011] This invention makes it possible to provide solutions to all or part of the problems of thickeners for aqueous compositions, particularly thickeners for hydroalcoholic compositions, in the prior art.

[0012] Therefore, the present invention provides a thickener P, which is prepared in the absence of acrylamide by at least one polymerization reaction of the following substances:

[0013] a. More than 30% to 69.75% by weight of at least one anionic monomer (a), selected from acrylic acid, acrylates, methacrylic acid, methacrylates, and combinations thereof;

[0014] b. 29.75% to less than 65% by weight of at least one nonionic monomer (b), which is selected from C1 to C8 esters of acids selected from acrylic acid, methacrylic acid, and combinations thereof;

[0015] c. 0.5% to 5% by weight of at least one compound of formula I (c):

[0016]

[0017] in:

[0018] *R 1 Independently representing H or CH3,

[0019] *R 2 and R 3 Whether the two are the same or different, they can independently represent H, CH3, or CH2CH3.

[0020] The weight percentages above are relative to the total weight of monomers (a), (b), and (c).

[0021] Also preferably according to the present invention, compound (b) is selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, vinyl acetate, and combinations thereof. More preferably according to the present invention, compound (b) is selected from ethyl acrylate, butyl acrylate, methyl methacrylate, and combinations thereof.

[0022] Also preferably according to the invention, compound (c) is a compound of formula I, wherein R 2 and R 3 H represents the compound. More preferably, according to the present invention, compound (c) is selected from N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and more preferably N-hydroxymethylacrylamide.

[0023] Also preferably according to the invention, the thickener P is completely or partially neutralized, preferably by at least one compound selected from NaOH, KOH, ammonium derivatives, ammonia, amine bases, such as triethanolamine or 2-amino-2-methyl-propanol (AMP), and combinations thereof. More preferably, the thickener P is neutralized by at least one compound selected from amine bases, such as triethanolamine or 2-amino-2-methyl-propanol (AMP).

[0024] Advantageously, according to the invention, the thickener P can also be completely or partially coagulated. Preferably, the thickener P is completely or partially coagulated by lowering the pH, for example by lowering the pH to less than 6.5, particularly by acidic compounds, especially by at least one organic or inorganic acid compound, particularly selected from phosphoric acid, citric acid, gluconolactone, lactic acid, salicylic acid, glycolic acid, ascorbic acid, glutamic acid, hydrochloric acid, acetic acid, D-gluconic acid, sulfonic acid, methanesulfonic acid, benzimidazole sulfonic acid, tartaric acid, 4-aminobenzoic acid, benzoic acid, sorbic acid, phenylbenzimidazole sulfonic acid, benzylidene camphor sulfonic acid, terephthalimide dicamphor sulfonic acid, kojic acid, and hyaluronic acid. Also preferably, the thickener P is completely or partially coagulated by increasing the ionic strength, for example by adding at least one ionized compound or at least one salt, particularly NaCl, KCl, MgCl2, CaCl2, MgSO4, CaSO4, or by adding phenylbenzimidazole sulfonic acid (PBSA) or sodium pyroglutamate (NaPCA), or even by adding at least one ionized organic sunscreen agent.

[0025] Preferably, according to the invention, the polymerization reaction uses a fraction of the total weight of monomers (a), (b), and (c).

[0026] -32.5% by weight to 64.75% by weight of monomer (a),

[0027] -34.75% by weight to 62.5% by weight of monomer (b), and

[0028] -0.5% by weight to 5% by weight of monomers (c).

[0029] The thickener P according to the invention is prepared from essential compounds (a), (b), and (c) in the absence of acrylamide. Compounds (a), (b), and (c) can be used alone or in combination with one or more other compounds or monomers. Particularly advantageously, the invention provides a thickener Pa prepared according to the invention solely from compounds (a), (b), and (c).

[0030] Also advantageously, the thickener P according to the invention is prepared by a polymerization reaction that also uses at least one specific additional compound.

[0031] According to the invention, the specific additional compound is a nonionic monomer (d) selected from C1 to C8 esters of acids selected from itaconic acid and maleic acid. Preferably, monomer (d) is selected from methyl itaconic acid, ethyl itaconic acid, propyl itaconic acid, butyl itaconic acid, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, and combinations thereof. Preferably, according to the invention, the amount of monomer (d) can be from 5% to 30% by weight of the nonionic monomer (b) used.

[0032] According to the present invention, another specific additional compound is compound (e) of formula II:

[0033]

[0034] in:

[0035] *T 1 and T 2 Whether the two are the same or different, they can be used independently to represent H or CH3.

[0036] *Q 1 and Q 2 Whether the two are the same or different, they can be used independently to represent H, CH3, or CH2CH3.

[0037] Preferably, according to the invention, compound (e) is prepared by a pre-reaction or in-situ reaction between at least one compound (a) as defined according to the invention and at least one compound (c) of formula (I). Advantageously, the polymerization reaction can use monomer (e) in amounts of less than 8 wt%, preferably from 0.2 wt% to 8 wt%, and particularly from 0.5 wt% to 5 wt%, relative to the total weight of the monomers.

[0038] According to the invention, another specific additional compound is compound (f), which is selected from 2-acrylamido-2-methylpropanesulfonic acid, ethoxymethacrylate sulfonate, sodium methacrylate sulfonate, styrene sulfonate / ester, hydroxyethyl phosphate acrylate, hydroxypropyl phosphate acrylate, hydroxyethylhexyl phosphate acrylate, hydroxyethyl methacrylate phosphate, hydroxypropyl methacrylate phosphate, hydroxyethylhexyl methacrylate phosphate, their salts, and combinations thereof. 2-acrylamido-2-methylpropanesulfonic acid is a preferred compound (f). Advantageously, the polymerization reaction can use monomer (f) in amounts of less than 20% by weight, preferably from 0.2% to 20% by weight, and particularly from 0.5% to 10% by weight relative to the total weight of the monomers.

[0039] According to the invention, another specific additional compound is a compound (g) selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxyethylhexyl methacrylate. Advantageously, the polymerization reaction can use less than 20% by weight, preferably from 0.2% to 20% by weight, and particularly from 0.5% to 10% by weight of monomer (g) relative to the total weight of the monomers.

[0040] According to the invention, another specific additional compound is a crosslinked monomer (h) or at least one monomer containing at least two olefinic unsaturated bonds. Advantageously, the polymerization reaction can use monomer (h) in amounts of less than 5% by weight, preferably 0.01% to 4% by weight, particularly 0.02% to 4% by weight or 0.02% to 2% by weight, particularly 0.02% to 1% by weight, relative to the total weight of the monomer.

[0041] According to the invention, another specific additional compound is an associating monomer (i), preferably compound (i) of formula III:

[0042] G 1 -(OE) m -(OP) n -G 2 (III)

[0043] in:

[0044] -m and n may be the same or different, independently representing 0 or an integer or decimal less than 150, where m or n is not equal to 0.

[0045] -EO independently represents the CH2CH2O group.

[0046] -PO independently represents a group selected from CH(CH3)CH2O and CH2CH(CH3)O.

[0047] -G 1This indicates a group containing at least one polymerizable olefinic unsaturated bond, preferably an acrylate group or a methacrylate group, and

[0048] -G 2 Indicates C6 to C6, whether straight or branched. 40 Alkyl, phenyl, polyphenyl, preferably straight-chain or branched C 10 To C 30 Alkyl groups, more preferably straight-chain or branched C4 groups 12 To C 22 Alkyl groups, or groups containing 2 to 5 phenyl groups, or tristyrylphenyl, or pentastyrylisopropylphenylphenyl.

[0049] Advantageously, the polymerization reaction can use less than 20% by weight, preferably from 0.05% to 20% by weight, and especially from 0.1% to 10% by weight of monomers relative to the total weight of monomers (i).

[0050] Advantageously, the present invention provides a thickener Pb prepared from compounds (a), (b), and (c), and at least one compound (f), wherein compound (f) is preferably 2-acrylamido-2-methylpropanesulfonic acid. Also advantageously, the present invention provides a thickener Pc prepared from compounds (a), (b), and (c), and at least one compound (i). Advantageously, the present invention provides a thickener Pd prepared from compounds (a), (b), and (c), and at least one compound (f), and at least one compound (i), wherein compound (f) is preferably 2-acrylamido-2-methylpropanesulfonic acid. Also advantageously, the present invention provides a thickener Pe prepared from compounds (a), (b), and (c), and at least one compound (h). Also advantageously, the present invention provides a thickener Pf prepared from compounds (a), (b), and (c), and at least one compound (e).

[0051] Preferably, the glass transition temperature of the thickener P according to the present invention is greater than -10°C or greater than 0°C. Preferably, the glass transition temperature of the thickener P is greater than 15°C or greater than 25°C. Even more preferably, the thickener P according to the present invention is a solid, more preferably a powder.

[0052] The preparation of thickener P according to the present invention may include the use of compound (e) of formula II. The present invention also provides compound (e) of formula II:

[0053]

[0054] in:

[0055] *T 1 and T 2 Whether the two are the same or different, they can be used independently to represent H or CH3.

[0056] *Q1 and Q 2 Whether the two are the same or different, they can be used independently to represent H, CH3, or CH2CH3.

[0057] Preferably, according to the present invention, compound (e) is a compound of formula II, wherein Q 1 and Q 2 H represents H.

[0058] Particularly preferably, the compound (e) according to the invention is selected from:

[0059] Compound (e1) of formula II, wherein T 1 T 2 Q 1 , and Q 2 H represents

[0060] Compound (e2) of formula II, wherein T 1 Indicates CH3, T 2 Q 1 , and Q 2 H represents

[0061] Compound (e3) of formula II, wherein T 2 Indicates CH3, T 1 Q 1 , and Q 2 H represents

[0062] Compound (e4) of formula II, wherein T 1 and T 2 Represents CH3, Q 1 , and Q 2 H represents H.

[0063] According to the present invention, compound (e3) is more particularly preferred.

[0064] The compound (e) according to the invention is preferably prepared by a condensation reaction of at least one compound (a) according to the invention with at least one compound (c) according to the invention.

[0065] Furthermore, the present invention also provides a method for preparing copolymers by polymerizing a compound (e) according to the invention with at least one polymerizable compound, particularly with at least one polymerizable compound selected from compounds (a), (b), and combinations thereof according to the invention, especially (H)ASE [(hydrophobic) alkali-swellable emulsion copolymers or alkali-swellable polymer emulsions capable of being hydrophobically treated]. The polymerization reaction may also use at least one other additional compound selected from compounds (c), (d), (f), (g), (h), (i), and combinations thereof according to the invention.

[0066] The thickener P according to the invention is a particularly effective thickener, especially for controlling the viscosity of aqueous compositions. Therefore, the invention provides a method for controlling the viscosity of an aqueous composition, comprising adding at least one thickener P according to the invention to the aqueous composition.

[0067] The resulting thickened aqueous composition is also part of this invention. Therefore, this invention also provides an aqueous composition C comprising water and at least one thickener P according to the invention. Preferably, according to the invention, composition C is selected from detergent compositions, hygiene product compositions, disinfectant compositions, cosmetic compositions, coating compositions, paper coating pigment compositions, textile printing and dyeing compositions, and textile coating compositions. According to the invention, preferred hygiene product compositions or disinfectant compositions are selected from antibacterial compositions, bactericidal compositions, biocidal compositions, bacteriostatic compositions, and antiviral compositions.

[0068] Preferably, according to the present invention, composition C further comprises at least one additive selected from alcohols, oxidizing compounds, emollient compounds, surfactant compounds, and combinations thereof. More preferably, according to the present invention, composition C further comprises at least one alcohol and optionally at least one additive selected from oxidizing compounds, emollient compounds, surfactant compounds, and combinations thereof. Preferably, according to the present invention, the alcohol used is selected from ethanol, n-propanol, isopropanol, and combinations thereof.

[0069] A more preferred composition C according to the present invention comprises:

[0070] *At least one thickener P, from 0.1% to 5% by weight.

[0071] *45% to 9.9% by weight of water,

[0072] *At least one alcohol, ranging from 50% to 90% by weight.

[0073] The thickener P according to the invention makes it possible to control the viscosity of aqueous compositions particularly effectively. Therefore, the invention provides composition C according to the invention, which has a Brookfield viscosity of 800 mPa·s to 20000 mPa·s, preferably 1000 mPa·s to 15000 mPa·s or 5000 mPa·s to 15000 mPa·s, measured at 25°C and 6 rpm.

[0074] Advantageously, the compositions of the present invention are in gel or foam form.

[0075] Composition C according to the invention can be used in various media, particularly in acidic or alkaline media. Preferably, the pH of composition C according to the invention is greater than 6 or greater than 6.5. More preferably, the pH of composition C according to the invention is less than 13, more preferably less than 12, and more preferably less than 11. More preferably, the pH of composition C according to the invention is 6 to 13, or 6 to 12, or 6 to 11; and even more preferably, the pH of composition C according to the invention is 6.5 to 13, or 6.5 to 12, or 6.5 to 11.

[0076] The present invention also provides a method for preparing an aqueous alcohol solution, comprising mixing in water at least one thickener P according to the invention and at least one alcohol and at least one additive optionally selected from oxidizing compounds, emollient compounds, surfactant compounds, and combinations thereof.

[0077] The specific, advantageous, or preferred features of the thickener P according to the invention enable the definition of compositions and various methods according to the invention, which are also specific, advantageous, or preferred.

[0078] The following examples illustrate various aspects of the invention. Unless otherwise stated, the reagents used are acrylic acid (AA), methacrylic acid (MAA), ethyl acrylate (EA), butyl acrylate (BuA), N-hydroxymethylacrylamide (NMA), and 2-acrylamido-2-methylpropanesulfonic acid (AMPS, in the form of a 50% aqueous solution of its sodium salt).

[0079] Example 1: Preparation and characterization of thickener P according to the present invention

[0080] Preparation and characterization of the copolymer (P1) according to the present invention

[0081] An initial load consisting of 460 g of deionized water and 2.3 g of sodium dodecyl sulfate was placed in the reactor.

[0082] In the first glass beaker, according to the proportions listed in Table 1, weigh out 121.37 g of monomer (a), 196.55 g of monomer (b), and 5.67 g of monomer of formula I (c), where R1 R 2 and R 3 The contents are H, 1.92g sodium dodecyl sulfate, and 145g deionized water.

[0083] In the second glass beaker, weigh out 0.270 g of ammonium persulfate and dissolve it in 45 g of deionized water.

[0084] The contents of the reactor were heated to 86℃±2℃.

[0085] The reagents in two beakers were injected into the polymerization reactor over a period of 2 hours and 30 minutes at a temperature of 86℃±2℃.

[0086] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0087] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0088] A copolymer (P1) with a solid content of 30.5% by weight was obtained, and its composition is shown in Table 1.

[0089] Preparation and characterization of the copolymer (P2) according to the present invention

[0090] An initial load consisting of 445g of deionized water and 2.3g of sodium dodecyl sulfate was placed in the reactor.

[0091] In the first glass beaker, according to the proportions listed in Table 1, weigh out 108.95 g of monomer (a), 184.12 g of monomer (b), 24.85 g of another monomer (b), and 5.67 g of monomer of formula I (c), where R 1 R 2 and R 3 The contents are H, 1.92g sodium dodecyl sulfate, and 140g deionized water.

[0092] In the second glass beaker, weigh out 0.270 g of ammonium persulfate and dissolve it in 45 g of deionized water.

[0093] The contents of the reactor were heated to 86℃±2℃.

[0094] The reagents in two beakers were injected into the polymerization reactor over a period of 2 hours and 30 minutes at a temperature of 86℃±2℃.

[0095] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0096] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0097] A copolymer (P2) with a solids content of 30.5% by weight was obtained, and its composition is shown in Table 1.

[0098] Preparation and characterization of the copolymer (P3) according to the present invention

[0099] An initial load consisting of 460 g of deionized water and 2.3 g of sodium dodecyl sulfate was placed in the reactor.

[0100] In the first glass beaker, according to the proportions listed in Table 1, weigh out 110.76 g of monomer (a), 185.95 g of monomer (b), 16.18 g of another monomer (b), and 5.67 g of monomer of formula I (c), where R 1 R 2 and R 3 The contents are H, 1.92g sodium dodecyl sulfate, and 145g deionized water.

[0101] In the second glass beaker, weigh out 0.270 g of ammonium persulfate and dissolve it in 45 g of deionized water.

[0102] The contents of the reactor were heated to 86℃±2℃.

[0103] The reagents in two beakers were injected into the polymerization reactor over a period of 2 hours and 30 minutes at a temperature of 86℃±2℃.

[0104] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0105] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0106] A copolymer (P3) with a solids content of 30.2% by weight was obtained, and its composition is shown in Table 1.

[0107] Preparation and characterization of the copolymer (P4) according to the present invention

[0108] An initial load consisting of 450 g of deionized water and 2.97 g of sodium dodecyl sulfate was placed in the reactor.

[0109] In the first glass beaker, according to the proportions listed in Table 1, weigh out 126.77 g of monomer (a), 158.25 g of monomer (b), and 4.46 g of monomer of formula I (c), where R 1 R 2 and R 3 Represents H, 7.90g of monomer (i) of formula III, wherein G 1 G represents the methacrylate group. 2 Represents a straight chain C 22Alkyl group, m represents 25 and n represents 0 (C22-EO25-methacrylate), 1.76 g sodium dodecyl sulfate, and 130 g deionized water.

[0110] The contents of the reactor were heated to 86℃±2℃.

[0111] In the second glass beaker, weigh out 0.194 g of ammonium persulfate and dissolve it in 40 g of deionized water.

[0112] The reagents in two beakers were injected into the polymerization reactor at a temperature of 86℃±2℃ over a period of 2 hours.

[0113] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0114] Then, bake for 30 minutes, allow the medium to cool, and then filter it.

[0115] A copolymer (P4) with a solids content of 30.4% by weight was obtained, and its composition is shown in Table 1.

[0116] Preparation and characterization of the copolymer (P5) according to the present invention

[0117] An initial load consisting of 445g of deionized water and 2.3g of sodium dodecyl sulfate was placed in the reactor.

[0118] In the first glass beaker, weigh out 106.43g of monomer (a), 181.61g of monomer (b), 24.85g of another monomer (b), 5.67g of monomer (c), 1.92g of sodium dodecyl sulfate, 140g of deionized water, and 5.03g of triallyl cyanurate, according to the proportions listed in Table 1.

[0119] In the second glass beaker, weigh out 0.270 g of ammonium persulfate and dissolve it in 50 g of deionized water.

[0120] The contents of the reactor were heated to 86℃±2℃.

[0121] The reagents in two beakers were injected into the polymerization reactor over a period of 2 hours and 30 minutes at a temperature of 86℃±2℃.

[0122] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0123] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0124] A copolymer (P5) with a solids content of 30.7% by weight was obtained, and its composition is shown in Table 1.

[0125] Preparation and characterization of the copolymer (P6) according to the present invention

[0126] An initial load consisting of 465 g of deionized water and 6.47 g of sodium dodecyl sulfate was placed in the reactor.

[0127] In the first glass container, according to the proportions listed in Table 1, weigh out 108.14 g of monomer (a), 184.11 g of monomer (b), and 2.89 g of monomer of formula I (c), where R 1 R 2 and R 3 The contents are H, 2.82 g sodium dodecyl sulfate, and 124.4 g deionized water.

[0128] In the second glass container, weigh out 0.914 g of ammonium persulfate and dissolve it in 10 g of deionized water.

[0129] In the third glass container, weigh 0.099 g of sodium metabisulfite and dissolve it in 10 g of deionized water. In the fourth container, such as a disposable syringe, weigh 5.13 g of a 50% by weight aqueous solution of sodium (f)2-acrylamido-2-methylpropanesulfonate monomer.

[0130] The contents of the reactor were heated to 76℃±2℃.

[0131] The reagents from four containers were injected into the polymerization reactor at a temperature of 86℃±2℃ over a period of 2 hours.

[0132] Then, 0.3g of ammonium persulfate dissolved in 20g of deionized water is injected into the reactor within 1 hour.

[0133] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0134] A copolymer (P6) with a solids content of 30.2% by weight was obtained, and its composition is shown in Table 1.

[0135] Preparation and characterization of the copolymer (P7) according to the present invention

[0136] An initial load consisting of 474.69 g of deionized water and 2.96 g of sodium dodecyl sulfate was placed in the reactor.

[0137] In the first glass beaker, according to the proportions listed in Table 1, weigh out 148.29 g of monomer (a), 159.95 g of monomer (b), and 2.44 g of monomer of formula I (c), where R 1 R 2 and R 3 Represents H, monomer (i) of formula III, where G 1 G represents the methacrylate group. 2 Represents a straight chain C 22Alkyl group, m represents 25 and n represents 0 (C22-EO25-methacrylate), 1.76 g sodium dodecyl sulfate, and 151.62 g deionized water.

[0138] The contents of the reactor were heated to 86℃±2℃.

[0139] In the second glass beaker, weigh out 0.194 g of ammonium persulfate and dissolve it in 22 g of deionized water.

[0140] The reagents in two beakers were injected into the polymerization reactor at a temperature of 86℃±2℃ over a period of 2 hours.

[0141] Then, 0.20g of ammonium persulfate dissolved in 20g of deionized water is injected into the reactor within 1 hour.

[0142] Then, bake for 30 minutes, allow the medium to cool, and then filter.

[0143] A copolymer (P7) with a solids content of 31.3% by weight was obtained, and its composition is shown in Table 1.

[0144]

[0145] Table 1

[0146] Example 2: Preparation and characterization of comparative copolymers

[0147] Preparation and characterization of comparative copolymers (CP1)

[0148] The synthesis method is similar to that used to prepare thickener P1. In the first glass container, 112.98 g of monomer (a), 159.13 g of monomer (b), 0.695 g of monomer (h) diallyl phthalate, 1.92 g of sodium dodecyl sulfate, and 140 g of deionized water were weighed according to the proportions listed in Table 2.

[0149] In the second glass beaker, weigh out 0.270 g of ammonium persulfate and dissolve it in 50 g of deionized water.

[0150] The contents of the reactor were heated to 86℃±2℃.

[0151] The reagents in two beakers were injected into the polymerization reactor over a period of 2 hours and 30 minutes at a temperature of 86℃±2℃.

[0152] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0153] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0154] A copolymer (CP1) with a solids content of 30.1% by weight was obtained, and its composition is shown in Table 2.

[0155] Preparation and characterization of comparative copolymer (CP2)

[0156] The synthesis method is similar to that used to prepare thickener P2. In the first glass beaker, according to the proportions listed in Table 2, 123.65 g of monomer (a), 165.30 g of monomer (b), and 11.50 g of monomer (i) of formula III were weighed, wherein G 1 G represents the methacrylate group. 2 Represents a straight chain C 22 Alkyl group, m represents 25 and n represents 0 (C22-EO25-methacrylate), 1.92 g sodium dodecyl sulfate, and 140 g deionized water.

[0157] In the second glass beaker, weigh out 0.270 g of ammonium persulfate and dissolve it in 50 g of deionized water.

[0158] The contents of the reactor were heated to 86℃±2℃.

[0159] The reagents in two beakers were injected into the polymerization reactor over a period of 2 hours and 30 minutes at a temperature of 86℃±2℃.

[0160] Then, 0.106g of ammonium persulfate dissolved in 20g of deionized water was injected into the reactor within 1 hour.

[0161] Then, bake for 1 hour, allow the medium to cool, and then filter it.

[0162] A copolymer (CP2) with a solids content of 30.0% by weight was obtained, and its composition is shown in Table 2.

[0163]

[0164] Table 2

[0165] Example 3: Preparation and characterization of the water-alcohol composition according to the present invention and a comparative water-alcohol composition.

[0166] The hydroalcoholic compositions C1 to C5 and CC1 and CC2 were prepared by mixing the thickeners P1 to P5 and the comparative copolymers CP1 and CP2 in water in the amounts shown in Table 3.

[0167]

[0168] Table 3

[0169] In a 250 mL beaker equipped with a stirrer with Rayneri blades of 40 mm in diameter, add the components of phase A until a homogeneous mixture is obtained.

[0170] While stirring, add the thickener or copolymer of phase B, followed by the neutralizer of phase C. Increase the stirring speed as viscosity increases, ensuring no air is introduced. After adding all the neutralizer, continue stirring for 10 minutes.

[0171] Then add the remaining ethanol from phase D and continue stirring for 10 minutes. Then, centrifuge the composition to remove any air bubbles.

[0172] Then, the viscosities of the water-alcohol compositions C1 to C5 and CC1 and CC2 were measured. The compositions were placed in a constant temperature bath at 25°C for 1 hour, and the viscosity was measured using a Brookfield viscometer at 6 rpm. The results are shown in Table 4.

[0173] Composition Thickeners or copolymers Brookfield viscosity (mPa·s) C1 P1 7 380 C2 P2 7 620 C3 P3 7 460 C4 P4 5 320 C5 P5 5 270 CC1 PC1 570 CC2 PC2 160

[0174] Table 4

[0175] The thickener P according to the invention enables the preparation of hydroalcohol compositions with high viscosity, which is essential for using these compositions. This viscosity control is achieved by preparing thickener P in the absence of acrylamide. Comparative copolymers cannot achieve acceptable viscosity in hydroalcohol compositions.

Claims

1. A thickener P, prepared in the absence of acrylamide by polymerization of at least one of the following substances: a. 32.5% to 64.75% by weight of at least one anionic monomer (a), selected from acrylic acid, acrylates, methacrylic acid, methacrylates, and combinations thereof; b. 34.75% to 62.5% by weight of at least one nonionic monomer (b), selected from ethyl acrylate, butyl acrylate and combinations thereof; c. 0.5% to 5% by weight of at least one compound of formula I (c): in: *R 1 Independently representing H or CH3, *R 2 and R 3 H represents The weight percentages above are relative to the total weight of monomers (a), (b), and (c); and Optionally, the polymerization reaction also uses at least one compound selected from: d. Nonionic monomer (d) selected from C1 to C8 esters of acids selected from itaconic acid and maleic acid, or e. Compounds of formula II (e): in: *T 1 and T 2 Whether the two are the same or different, they can be used independently to represent H or CH3. *Q 1 and Q 2 Same or different, independently representing H, CH3, or CH2CH3, or f. At least one compound (f) selected from 2-acrylamido-2-methylpropanesulfonic acid, ethoxymethacrylate sulfonate, sodium methacrylate sulfonate, styrene sulfonate / ester, hydroxyethyl phosphate, hydroxypropyl phosphate, hydroxyethylhexyl phosphate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl phosphate, salts thereof, and combinations thereof. g. At least one compound (g) selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, or h. A crosslinked monomer (h) or at least one monomer containing at least two olefinic unsaturated bonds, or i. At least one associating monomer (i).

2. The thickener P according to claim 1, wherein compound (c) is N-hydroxymethylacrylamide.

3. The thickener P according to any one of claims 1 or 2, wherein the thickener P is completely or partially neutralized.

4. The thickener P according to any one of claims 1 or 2, which is completely or partially coagulated.

5. The thickener P according to any one of claims 1 or 2, wherein: Compound (f) is 2-acrylamido-2-methylpropanesulfonic acid, or Monomer (i) is a compound of formula (III): G 1 -(EO) m -(PO) n -G 2 (III) in: -m and n may be the same or different, independently representing 0 or an integer or decimal less than 150, where m or n is not equal to 0. -EO independently represents the CH2CH2O group. -PO independently represents a group selected from CH(CH3)CH2O and CH2CH(CH3)O. -G 1 It represents a group containing at least one polymerizable olefinic unsaturated bond, and -G 2 Indicates C6 to C6, whether straight or branched. 40 Alkyl, phenyl, or polyphenyl.

6. The thickener P according to any one of claims 1 or 2, which is prepared only from compounds (a), (b), and (c).

7. The thickener P according to any one of claims 1 or 2 has a glass transition temperature greater than -10°C.

8. The thickener P according to any one of claims 1 or 2, wherein it is a solid.

9. An aqueous composition C comprising water and at least one thickener P according to any one of claims 1 to 8.

10. The composition C according to claim 9, wherein it is selected from cleaning agent compositions, hygiene product compositions, disinfectant compositions, cosmetic compositions, coating compositions, paper coating pigment compositions, textile printing and dyeing compositions, and textile coating compositions.

11. The composition C according to any one of claims 9 or 10, further comprising at least one additive selected from alcohols, oxidizing compounds, emollient compounds, surfactant compounds, and combinations thereof.

12. The composition C according to any one of claims 9 or 10, wherein the Brookfield viscosity, measured at 25°C and 6 rpm, is from 800 mPa·s to 20000 mPa·s.

13. The composition C according to any one of claims 9 or 10, wherein the pH is 6 to 13.

14. A method for controlling the viscosity of an aqueous composition, comprising adding at least one thickener P according to any one of claims 1 to 8 to the aqueous composition.

15. A method for preparing an aqueous alcohol solution, comprising mixing in water at least one thickener P according to any one of claims 1 to 8 and at least one alcohol and optionally at least one additive selected from oxidizing compounds, emollient compounds, surfactant compounds, and combinations thereof.

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