EP1812482A1

EP1812482A1 - Substituted cumyl phenols, use thereof in a copolymerisation method copolymers thus obtained and use thereof as thickeners

Info

Publication number: EP1812482A1
Application number: EP05815281A
Authority: EP
Inventors: Denis Ruhlmann; Jean-Marc Suau
Original assignee: Coatex SAS
Current assignee: Coatex SAS
Priority date: 2004-11-04
Filing date: 2005-10-28
Publication date: 2007-08-01
Also published as: FR2877336B1; WO2006048539A1; TW200621809A; FR2877336A1

Abstract

The invention relates to associative thickeners, and more particularly, HASE type associative thickeners used in aqueous formulations, firstly concerning novel hydrophobic compounds of the radical-substituted cumyl phenol type, produced by the reaction of a cumyl phenol and an alkene or a mixture of alkenes. Said products can be used in the composition of novel associative HASE type thickeners, which permit an improvement in the rheology of aqueous formulations to which they are applied.

Description

SUBSTITUTED CUMYL PHENOLS, THEIR USE IN A PROCESS

OF COPOLYMERIZATION, COPOLYMERS OBTAINED AND THEIR

USE AS THICKENERS

The present invention relates to the sector of associative thickeners, and more particularly associative thickeners of the HASE type (Hydrophobically modified and alkaline-thickening modified emulsions or Hydrophobically modified Alkali-Soluble Emulsions), used in aqueous formulations.

The invention firstly relates to novel hydrophobic compounds of the substituted cumyl phenols type, of general formula (I):

(I) wherein R denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes, and i denotes an integer between 1 and 5.

The invention also relates to the process for obtaining said hydrophobic compounds of formula (I) by an alkylation reaction of cumyl phenol.

The invention also relates to the use of such compounds in a process for the synthesis of water-soluble copolymers, said copolymers being the result of the copolymerization of at least one ethylenic and carboxylic functional monomer, at least one ethylenically unsaturated monomer and without carboxylic function, at least one nonionic monomer comprising a hydrophobic group based on new compounds of the type cumyl substituted phenols of formula (I), and optionally at least one crosslinking monomer.

The invention also relates to novel water-soluble copolymers, said copolymers being the result of the copolymerization of at least one ethylenic and carboxylic functional monomer, of at least one monomer with ethylenic unsaturation and without carboxylic function, of at least one monomer nonionic composition comprising a hydrophobic group based on the novel substituted cumyl phenols compounds of formula (I), and optionally at least one crosslinking monomer.

The invention also relates to the use as thickeners of said water-soluble copolymers, in aqueous formulations, in particular in the sectors of aqueous paints, inks and varnishes, paper and in particular in paper coating coatings, in printing formulations. textile, for detergents, cosmetics, drilling muds, cement and ceramics.

The invention also relates to the thickeners obtained.

The invention finally relates to aqueous formulations containing said copolymers, and in particular aqueous paints, inks and varnishes, paper formulations and in particular coating colors, formulations for textile printing, detergent formulations, cosmetic formulations, slurries and the like. drilling, cements and ceramics.

The aqueous paint formulations containing mineral fillers consist of a liquid phase which may be water or water mixed with one or more organic solvents which may or may not be miscible in water, of one or more polymers in water. emulsion in the liquid phase, termed binders, of fillers and / or pigments, of at least one dispersing agent for the fillers and / or of the elements which must have been a water-soluble copolymer or copolymer, of adjuvants as diverse as surfactants , coalescing agents, biocides, antifoam or other, and finally at least one thickening agent which is a polymer or a natural or synthetic copolymer. The thickening agent makes it possible to control the rheology of said formulations, and in particular aqueous paints, both at the manufacturing stage, during their transport, their storage or during their implementation. The diversity of practical constraints at each of these stages refers to a multiplicity of different rheological behaviors. Nevertheless, it is possible to summarize the need of those skilled in the art to obtain a thickening effect of the aqueous formulation, both for reasons of stability over time, and for a possible application of the paint on a surface. vertical, the absence of splashing at the time of implementation, etc. This is why we have designated the additives that contribute to this regulation of the rheological behavior under the term thickeners.

If one seeks to understand more precisely the constraints in terms of rheology that are posed to the formulator of aqueous paints, it can be indicated in a first step that the skilled person - the manufacturer of thickeners - knows that the rheological profile of said formulations, well known by him, is represented by the curve of the viscosity η as a function of the shear gradient D.

It is recalled that the relation between the viscosity η and the shear gradient D is given by the following formula:

η (Pa.s) = Constraint (Pa) / Gradient D (s ^"1 )

The stress is a measure of the pressure applied to the aqueous formulation.

In the field of aqueous paints, those skilled in the art know that the major difficulty encountered by the aqueous paint formulator is to simultaneously obtain:

a good "dynamic" behavior, ie a high viscosity with a high shear gradient: this translates in practice the requirement of a sufficiently high viscosity remaining during the step of applying the paint to the support, this application naturally implies a high shear rate; the benefits can be a higher build-up (ie, deposited thickness) and reduced splash propensity;

and

a good "static" behavior, ie a high viscosity for a low to medium shear gradient: this makes it possible in particular to ensure good stability of said paints during their storage while avoiding the phenomenon of sedimentation and a limitation of the tendency to sag on vertical support.

Since the invention aims to provide compositions which make it possible to obtain this dual rheological behavior, the Applicant here specifies what is meant by low, medium and high shear gradients, and indicates that reference will be made to these gradient domains of shear throughout the remainder of this application:

- 0 <D <20 s ^"1 : low shear gradient

- 20 s ^"1 <D <1000 s ^{" 1} : mean shear gradient

- 1000 s ^"1 <D <10 000 s ^{' 1} : high shear gradient

The viscosities at low, medium, and high shear rate will be measured in the present application respectively through the Brookfield ™ viscosity at 10 rpm, the Stormer viscosity, and the ICI viscosity, which are quantities perfectly known to man. of the trade, as well as the techniques that make it possible to measure them.

The operating mechanism and characteristics of associative thickeners are now well known and described in particular in the documents "Rheology modifiers for water-borne paints" (Surface Coatings Australia, 1985, pp. 6-10) and "Rheological modifiers for water". The most flexible tools for your formulations "(Eurocoat 97, UATCM, Vol 1, pp 423-442). These associative thickeners are water-soluble polymers having insoluble hydrophobic groups. Such macromolecules have a character associating: once introduced in water, the hydrophobic groups are likely to assemble in the form of micellar aggregates. These aggregates are interconnected by the hydrophilic parts of the polymers: there is then formation of a three-dimensional network which causes the increase of the viscosity of the medium.

Among these thickeners, one distinguishes the thickeners of the HEUR type (Ethylene oxide modified ethylene oxide or Hydrophobically modified ethylene oxide URethane), HMHEC (hydrophobically modified Hydroxyethylcellulose or Hydrophobically Modified Hydroxyethylcellulose) and HASE (Hydrophobically modified and thickening emulsions in alkaline medium or Hydrophobically modified Alkali-soluble Emulsions).

HASE thickeners are copolymers having an ionic monomer (in particular methacrylic acid), a nonionic monomer (such as ethyl acrylate) and a hydrophobic monomer, as recalled in US Pat. "The role of surfactants in HASE thickener rheology" (Polymeric Materials Science and Engineering, 67, 1992, pp. 280-281).

The influence of the hydrophobic monomer on the rheological properties induced by thickeners of HASE type has been widely reported in the literature, in the case of aqueous paints, and for hydrophobic groups of alkyl type, branched or unbranched. Thus, the documents "Dynamic light scattering of hydrophobically modified semi-dilute HASE solutions with varying length of hydrophobic alkyl chains" (Macromol Chem Phys., 203, 2002, pp. 2312-2321), and "Light scattering of dilute HASE solutions: effects of hydrophobicity and spacer length of macromonomer "(Macromolecules, 33, 2000, pp. 7021-7028) which focus on HASE type thickeners whose hydrophobic monomer is an alkyl chain having from 1 to 20 carbon atoms, teach that the low shear rate viscosity increases drastically for these additives, as soon as the number of carbons in the hydrophobic group is greater than 16. As for the document "Viscoelastic properties of HASE emulsion in knows solutions" (Polymer 40, 1999, pp. 6369-6379), which relates to thickeners of the HASE type whose hydrophobic group is an alkyl chain having from 8 to 20 carbon atoms, it demonstrates that whatever is the shear gradient considered, the viscosity increases very significantly with the number of carbon atoms carried by the alkyl chain. Finally, the document "Rheological properties of hydrophobically modified alkali-soluble polymers - effect of ethylene-oxide chain length" (Journal of Polymer Science: Part B: Polymer Physics, 36, 1998, pp 2275-2290) demonstrates that it is possible to manufacture associative thickeners of the HASE type having a hydrophobic group which may contain up to 32 carbon atoms.

Thus, the overall teaching provided by these documents is that in order to obtain more efficiency, whatever the shear gradient, one solution consists in increasing the number of carbon atoms borne by the hydrophobic group, in the case where the is an alkyl chain. Moreover, and the Applicant indicates that this is one of the general knowledge of the skilled person: for a given type of hydrophobic group, if we increase the number of carbon atoms, we will increase the viscosity of the aqueous formulation. Indeed, the size of the hydrophobic groups will condition the size of the micellar aggregates that they generate once in solution, which is directly related to an increase in viscosity, as recalled in the document "Rheology modifiers for water-borne paints" (Surface Coatings Australia,

1985, pp. 6-10).

In the manufacture of associative thickeners of the HASE type, those skilled in the art have also developed hydrophobic structures other than the alkyl chains.

Thus, the document EP 0 011 806 describes emulsion liquid polymers used as thickeners for aqueous compositions, and in particular latex paints, resulting from the copolymerization of a carboxylic acid-based monomer, a monomer which is ethyl acrylate or its mixtures with another monomer, and finally an alkyl-terminated nonionic surfactant ester having from 8 to 20 carbon atoms, or a phenyl alkyl chain having from 8 to 16 carbon atoms. These polymers prove to be effective at medium and high shear rates, as evidenced respectively by Stormer (mean shear gradient) and Haake (high shear rate equal to 10,000 s ^-1 ) viscosity measurements made for this type of polymer. . EP 0 013 836 teaches the existence of copolymers obtained by emulsion copolymerization of acrylic or methacrylic acid, a methacrylate or an alkyl acrylate, and a nonionic monomer terminated by an alkyl group. alkylaryl or polycyclic alkyl having 8 to 30 carbon atoms. Such additives make it possible to improve the storage behavior of the aqueous formulations, that is to say to improve the low shear rate viscosity, as indicated by the Brookfield viscosity values measured at 10 rpm.

EP-B-0 577 526 discloses copolymers which are obtained by the copolymerization of an ethylenic and carboxylic functional monomer, optionally an ethylenically unsaturated monomer and no carboxylic function, and an unsaturated oxyalkylated monomer. ethylenic and terminated with a hydrophobic fatty chain, itself consisting of linear or branched groups of the alkyl, alkylaryl, arylalkyl or aryl type having from 26 to 30 carbon atoms. Such thickeners are particularly effective in developing high viscosities under low shear rates in aqueous formulations.

Similarly, the document EP 1 270 617 describes copolymers of identical structure, which give the aqueous formulations a similar rheological profile, said polymers having a fatty chain consisting of linear or branched alkyl, alkylaryl, arylalkyl or aryl groups which can have up to 36 carbon atoms.

In parallel, the document EP 0 705 852 describes a rheological additive which is a copolymer obtained by the copolymerization of one or more carboxylic acid monomers, one or more nonionic vinyl monomers, one or more monomers. nonionic compounds containing an aralkyl-substituted hydrophobic phenol group, such as tristyrylphenol which has 30 carbon atoms. (The Applicant indicates that this compound is already well known for its surfactant properties, as evidenced by the document WO 97/03242 which describes a composition for absorbing UV radiation, containing especially di- and tristyrylphenols as surfactants). Such thickeners give aqueous paints a good rheological behavior with a high and medium speed gradient. Finally, the document US Pat. No. 5,292,828 describes thickeners the associative nature of which is exacerbated by the presence of several hydrophobic groups connected to the backbone of the polymer, which constitutes another method for increasing the number of carbon atoms on the hydrophobic part of said thickeners. Such thickeners improve the viscosity of aqueous low shear rate formulations, as evidenced by the Brookfield viscosity values reported herein.

These latter documents demonstrate that the skilled person has managed to develop hydrophobic structures other than alkyl chains, while increasing the number of carbon atoms borne by said hydrophobic groups, which generally make it possible to manufacture thickeners with a profile. rheological advantage than that obtained with thickeners having a simple alkyl chain.

Nevertheless, none of these solutions is satisfactory to those skilled in the art. Indeed, the prior art does not disclose any thickener capable of improving the rheology of aqueous formulations as low shear gradient, medium gradient or high. On the other hand, no document of the technique accessible to those skilled in the art does not mention thickeners HASE type having a hydrophobic group having more than 40 carbon atoms.

Consequently, there is still a need for those skilled in the art to develop HASE type thickeners having original hydrophobic structures and having a higher number of carbon atoms than in the prior art, and especially greater than 40: until today, no document shows that the skilled person has reached such a result.

Finally, it is a fundamental need for those skilled in the art to develop new hydrophobic structures, making it possible to synthesize thickeners of the HASE type, leading to an increase in the viscosity of the medium irrespective of the shearing gradient. Continuing its research in this field, the Applicant has surprisingly discovered new hydrophobic compounds of the type cumyl substituted phenols, obtained by a synthesis process by alkylation of cumyl phenol. On the one hand, these compounds prove to be new and on the other hand, their manufacturing process is very easy to implement: it is carried out at a temperature below 50 ^° C., is catalyzed by a Lewis acid which is preferably the compound of formula BF ₃ , and uses conventional solvents such as aromatic solvents and preferably toluene. Finally, such a process is a very simple method to develop to produce derivatives of cumyl phenol having more than 40 carbon atoms, and for some more than 50 carbon atoms: as the Applicant will explain in detail later, these The products are used in the composition of associative thickeners of the HASE type at the level of the hydrophobic group.

The Applicant has thus discovered as surprisingly that such substituted cumyl phenol compounds can be used in the synthesis of HASE type thickeners. To do this, they must first be ethoxylated and then rendered polymerizable by addition of unsaturation, according to techniques well known to those skilled in the art. Subsequently, they are polymerized with an ethylenic monomer and carboxylic function, and a monomer ethylenically unsaturated and without carboxylic function, and optionally a crosslinking monomer.

The Applicant has finally discovered that the resulting products turn out to be associative thickeners of the HASE type making it possible to increase the viscosity of the aqueous formulations in which they are used, at low, medium or high shearing gradient: the new and original structures developed by the Applicant thus meet the major requirement of the skilled person. In addition, some of the structures developed by the Applicant, involving new hydrophobic groups having more than 40 carbon atoms, offer particularly improved rheological behavior, which was another goal sought by the skilled person.

The novel hydrophobic compounds of the cumyl phenols substituted type according to the invention are therefore obtained by an alkylation reaction of cumyl phenol. Several documents already describe the conditions of this reaction, but only in the case of an alkylation reaction between styrene and phenol or phenyl ethyl phenols.

Thus, these conditions are described in US Pat. No. 2,432,356, which teaches the preparation at a temperature of between 120 ° C. and 200 ° C. of substituted phenols, by reaction of styrene with phenol, in the presence of a mixture containing a part of the sulfuric acid, and a phenolic compound belonging to the class of ortho- (alpha-phenylethyl) phenol and para- (alpha-phenylethyl) phenol.

They are also presented in the document "Kinetics of Phenol and Styrene Reaction in the Presence of Ethyl Etharate of Boron Fluoride" (Neftechemia, IX, 3, 1969), which describes the styrene-phenol addition reaction, catalysed at 25.degree. ° C with the compound of formula (C ₂ H 5) ₂ O ° BF ₃ .

Similarly, the document "Alkylation of phenol with styrene over Na _x H _3-x PW ₂ O ₄₀ " (Journal of Nanjing Normal University, 23, 4, 2000, pp. 62-66) studies the conditions of this same catalyzed reaction. by particular compounds of the Na _x H _{3 type} . _x PW ₁₂ O ₄₀ .

These new hydrophobic compounds, once ethoxylated, are rendered polymerizable by addition of ethylenic unsaturation according to techniques well known to those skilled in the art. This ethylenic unsaturation is of the acrylic, methacrylic, maleic, itaconic, crotonic, vinylic, allylic, or unsaturated ethylenic urethane, unsaturated amide or imide type, or any other radical-polymerizable ethylenic unsaturation.

These novel hydrophobic compounds then enter into the synthesis of novel copolymers according to the invention: they are polymerized with at least one ethylenic and carboxylic functional monomer, at least one ethylenically unsaturated monomer and no carboxylic function and optionally at least one monomer comprising at least one minus two ethylenic unsaturations.

These copolymers are manufactured by copolymerization techniques well known to those skilled in the art, in direct or inverse emulsion, in solution or else by precipitation. Examples of such syntheses are given in the following documents.

US 4,384,096 discloses a direct emulsion manufacturing process, which comprises reacting an unsaturated carboxylic acid monomer, a copolymerizable nonionic monomer and finally a vinyl monomer. An effective thickener is then obtained at pHs between 5.5 and 10.5. Similarly, the document EP 0216 479 discloses a process for the polymerization of an oil-in-water type emulsion thickener, which involves an unsaturated ethylenic ionic monomer, an unsaturated ethylenic non-ionic monomer which is insoluble in water, a particular unsaturated ethylenic monomer and optionally a crosslinking agent.

It is also possible to use inverse emulsion polymerization methods, such as that mentioned in the document EP 896 966. An associative acrylic polymer is manufactured here by polymerizing in inverse emulsion a mixture of at least one neutral, anionic or ethylenic monomer. cationic firstly, an acrylic monomer containing a tristyryl phenol group on the other hand, and finally optionally a polyunsaturated monomer in the presence of a surfactant.

There are also precipitation polymerization techniques. Thus, EP 0 333 499 describes the synthesis of an associative polymer used as a thickener in aqueous formulations. The process consists of dissolving the monomer mixture (an unsaturated ethylenic associative monomer and optionally another unsaturated ethylenic monomer) in a reaction medium, and carrying out the polymerization in this medium where the polymer particles will precipitate.

Solution polymerization methods can also be employed. As such, the document US Pat. No. 5,863,996 indicates a solution polymerization method for obtaining crosslinked particles of a size of less than 0.2 μm and a molecular weight of between 5,000 and 2,000,000, the reaction having in a solvent with well-defined solubility parameters. The product obtained is used as excipient in pharmaceutical tablets, but may also serve as a viscosity control agent.

Said copolymers thus prepared then act as associative thickeners of the HASE type which are very effective in aqueous formulations, which may, on the one hand, have a hydrophobic group having a very high number of carbon atoms (> 40), which the person skilled in the art has never managed to achieve until then, and conferring on the other hand a rheological behavior particularly interesting to said formulations, since they allow to increase very substantially the viscosity, as well as low, medium and high shear rate.

A first object of the invention therefore resides in new hydrophobic compounds of the cumyl substituted phenol type, of formula (I):

where R denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes,

and i denotes an integer between 1 and 5.

Preferably, R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, octadecene and vinyl acetate and their mixtures, and i is between 1 and 5. More preferably, R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, octadecene, vinyl acetate and their mixtures, and i is between 3 and 5.

Even more preferably, R denotes the radical resulting from the reaction between cumyl phenol and styrene, and i is equal to 5.

Another object of the invention is a process for synthesizing said compounds of formula (I) by an alkylation reaction of cumyl phenol, involving cumyl phenol and an alkene or a mixture of alkenes.

Preferably, R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, octadecene, vinyl acetate and their mixtures, and i is between 1 and 5.

More preferably, R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, octadecene, vinyl acetate and their mixtures, and i is between 3 and 5.

This process is characterized in that the synthesis temperature is between 25 ° C and 50 ° C, in that the catalyst is a Lewis acid and preferably the compound of formula BF ₃ , and in that the synthesis solvent is an aromatic solvent and preferably toluene.

Another subject of the invention is the use of compounds of formula (I) in a copolymerization process involving, that is to say, copolymerizing:

a) at least one monomer containing ethylenic unsaturation and with a carboxylic function,

b) at least one ethylenically unsaturated nonionic monomer, c) at least one ethylenically unsaturated oxyalkylated monomer constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), rendered polymerizable by adding an ethylenic unsaturation,

d) and optionally at least one monomer called crosslinking monomer, comprising at least two ethylenic unsaturations.

This use is also characterized in that:

a) the ethylenically unsaturated monomer (s) containing a carboxylic function are chosen from ethylenically unsaturated and monocarboxylic functional monomers such as acrylic or methacrylic acid, or also diacid semiesters such as C ₁ -C ₄ monoesters; maleic or itaconic acids, or mixtures thereof, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as anhydride. maleic, and more preferably in that the monomer with ethylenic unsaturation and carboxylic function is methacrylic acid,

b) the ethylenically unsaturated nonionic monomer or monomers are chosen from esters, amides or nitriles of acrylic and methacrylic acids, such as methyl, ethyl, butyl, 2-ethyl-hexyl or methyl acrylates or methacrylates, or acrylonitrile, vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, and more preferably in that the ethylenically unsaturated nonionic monomer is ethyl acrylate,

c) the ethylenically unsaturated oxyalkylated monomer or monomers constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), rendered polymerizable by addition of an ethylenic unsaturation, have the following formula (II):

(H) wherein:

m and p represent a number of alkylene oxide units ranging from 0 to 150, n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that <(m + n + p) q <150, and preferentially such that <(m + n + ρ) q <120, R ₁ represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

R 'represents a radical containing a polymerizable unsaturated functional group, belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, as well as to the group of unsaturated urethanes such as acrylurethanes, methacrylurethane, α α-dimethylisopropenyl-benzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,

R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, vinyl acetate, octadecene and their mixtures and i is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene, vinyl acetate, octadecene and their mixtures and is between 3 and 5, and even more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene and i is equal to 5, d) the optional monomer or monomers, referred to as crosslinking monomers, comprising at least two ethylenic unsaturations are chosen from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allylic ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

This use is also characterized in that the said copolymer is the result of the copolymerization, expressed by weight of the monomers, of:

a) 2 to 95%, and preferably 5 to 90% of at least one ethylenically unsaturated monomer containing a carboxylic function chosen from monomers containing ethylenic unsaturation and monocarboxylic functional groups, such as acrylic or methacrylic acid, or even diacid hemiesters such as C ₁ -C ₄ monoesters of maleic or itaconic acids, or mixtures thereof, or selected from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or still anhydrides of carboxylic acids, such as maleic anhydride, and more preferably from 2 to 95%, and preferably from 5 to 90% of methacrylic acid,

b) 2% to 95%, and preferably 5% to 90% of at least one ethylenically unsaturated nonionic monomer are chosen from esters, amides or nitriles of acrylic and methacrylic acids, such as acrylates or methacrylates methyl, ethyl, butyl, 2-ethylhexyl, or from acrylonitrile, vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, and more preferably from 2% to 95%, and preferably from 5% to 90% of ethyl acrylate,

c) 2% to 25% and preferably 5% to 20% of at least one oxyalkylated monomer containing ethylenic unsaturation, constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), made polymerizable by adding an ethylenic unsaturation, have the following formula (II):

(H) in which: m and p represent a number of alkylene oxide units ranging from 0 to

150, n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that 5 <(m + n + p) q <

150, and preferentially such that <(m + n + p) q <120,

R ₁ represents the methyl or ethyl radical,

R ₂ represents the methyl or ethyl radical,

R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, vinyl acetate, octadecene and their mixtures and i is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene, vinyl acetate, octadecene and their mixtures and i is between 3 and 5, and even more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene and i is equal to 5,

d) 0% to 3% of at least one crosslinking monomer comprising at least two ethylenic unsaturations are selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, acrylate allyl, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allylic ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

the total weight of monomers a), b), c) and d) being equal to 100%.

This use is also characterized in that the copolymerization process is a process in direct emulsion, or inverse, or in solution, or by precipitation.

Another object of the invention is the novel copolymers which are the result of the copolymerization:

a) at least one monomer with ethylenic unsaturation and with a carboxylic function,

b) at least one ethylenically unsaturated nonionic monomer,

c) at least one ethylenically unsaturated oxyalkylated monomer constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), rendered polymerizable by adding an ethylenic unsaturation,

These copolymers are also characterized in that: a) the monomer (s) with ethylenic unsaturation and with a carboxylic function are chosen from ethylenically unsaturated and monocarboxylic functional monomers such as acrylic or methacrylic acid, or else diacid hemiesters such as the C ₁ -C ₄ monoesters of maleic or itaconic acids, or mixtures thereof, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride. and more preferably in that the monomer with ethylenic unsaturation and with a carboxylic function is methacrylic acid,

b) the ethylenically unsaturated nonionic monomer or monomers are chosen from esters, amides or nitriles of acrylic and methacrylic acids, such as methyl, ethyl, butyl or 2-ethyl-hexyl acrylates or methacrylates, or from acrylonitrile; vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, and more preferably in that the ethylenically unsaturated nonionic monomer is ethyl acrylate,

(H) wherein: m and p represent a number of alkylene oxide units ranging from 0 to 150, n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that 5 <(m + n + p) q <150, and preferentially such that <(m + n + p) q <120, R 1 represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, vinyl acetate, octadecene and their mixtures and i is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene, vinyl acetate, octadecene and their mixtures and is between 3 and 5, and even more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene and i is equal to 5,

the optional monomer or monomers, referred to as crosslinking monomers, comprising at least two ethylenic unsaturations are chosen from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, allyl acrylate and methylene bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allylic ethers obtained from polyols selected from pentaerythritol, sorbitol or sucrose. These novel copolymers are also characterized in that they are the result of the copolymerization, expressed by weight of the monomers, of:

a) from 2% to 95%, and preferably from 5% to 90%, of at least one ethylenically unsaturated monomer containing a carboxylic function chosen from monomers containing ethylenic unsaturation and monocarboxylic functional groups, such as acrylic or methacrylic acid, or the diacid hemiesters such as the C 1 to C ₄ monoesters of maleic or itaconic acids, or mixtures thereof, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic, isocrotonic, cinnamic, itaconic and maleic acid, or else anhydrides of carboxylic acids, such as maleic anhydride, and more preferably from 2 to 95%, and preferably from 5 to 90% of methacrylic acid,

b) 2% to 95%, and preferably 5% to 90% of at least one ethylenically unsaturated nonionic monomer are chosen from esters, amides or nitriles of acrylic and methacrylic acids, such as acrylates or methacrylates methyl, ethyl, butyl, 2-ethylhexyl, or from acrylonitrile, vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, and more preferably from 2 to

95%, and preferably 5 to 90% of ethyl acrylate,

c) 2% to 25% and preferably 5% to 20% of at least one oxyalkylated monomer containing ethylenic unsaturation, constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), made polymerizable by adding an ethylenic unsaturation have the following formula (II):

(H) in which :

m and p represent a number of alkylene oxide units ranging from 0 to 150,

n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that 5 <(m + n + p) q ≤

150, and preferentially such that <(m + n + p) q <120,

- R ₁ represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

R 'represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters as well as to the group of urethane unsaturates such as acrylurethanes and methacrylurethanes; α-α-dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,

0% to 3% of at least one crosslinking monomer comprising at least two ethylenic unsaturations are selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate and trimethylolpropane trimethacrylate; allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allyl ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

the total weight of monomers a), b), c) and d) being equal to 100%.

In a variant which is also preferred, this copolymer results from a copolymerization which does not involve the crosslinking monomer d).

Another subject of the invention is the use of the copolymers according to the invention as thickeners in aqueous formulations, in particular in the sectors of aqueous paints, inks and varnishes, paper and in particular in paper coating coatings, in formulations for textile printing, for detergents, cosmetics, drilling muds, cement and ceramics.

This use is also characterized in that 0.01% to 5% by dry weight of the copolymers according to the invention are used relative to the total weight of said aqueous formulations, and more preferably in that it is used. from 0.05% to 3% by dry weight of the copolymers according to the invention relative to the total weight of said aqueous formulations.

Another object of the invention is the new thickeners which are the result of the copolymerization:

b) at least one ethylenically unsaturated nonionic monomer,

d) and optionally at least one monomer called crosslinking monomer, comprising at least two ethylenic unsaturations. These thickeners are also characterized in that:

a) the monomer (s) with ethylenic unsaturation and with a carboxylic function are chosen from ethylenically unsaturated and monocarboxylic functional monomers such as acrylic or methacrylic acid, or else diacid hemiesters such as the C ₁ -C ₄ monoesters of maleic or itaconic acids, or mixtures thereof, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride. and more preferably in that the monomer with ethylenic unsaturation and with a carboxylic function is methacrylic acid,

(H)

in which : m and p represent a number of alkylene oxide units ranging from 0 to 150,

n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that 5 <(m + n + p) q <150, and preferentially such that <(m + n + ρ) q <120,

R 1 represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

the optional monomer or monomers, referred to as crosslinking monomers, comprising at least two ethylenic unsaturations are chosen from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, allyl acrylate and methylene bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallylcyanurate, allyl ethers obtained from polyols selected from pentaerythritol, sorbitol, or sucrose.

These new thickeners are also characterized in that they are the result of copσlymerization, expressed as the weight of the monomers, of:

b) 2% to 95%, and preferably 5% to 90% of at least one ethylenically unsaturated nonionic monomer are chosen from esters, amides or nitriles of acrylic and methacrylic acids, such as acrylates or methacrylates methyl, ethyl, butyl, 2-ethyl-hexyl, or from acrylonitrile, vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, and more preferably from 2 to 95%, and preferably from 5 to 90% of ethyl acrylate,

c) 2% to 25% and preferably 5% to 20% of at least one oxyalkylated monomer containing ethylenic unsaturation, constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), made polymerizable by addition of a ethylenic unsaturation, have the following formula (II):

(H) wherein:

m and p represent a number of alkylene oxide units ranging from 0 to 150, n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that <(m + n + p) q <150, and preferentially such that <(m + n + p) q <120, R ₁ represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, vinyl acetate, octadecene and their mixtures and i is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol ^{~ and} tyfèrie, T ^' acëfâtè ^~ vinyl, octadécène and their mixtures and i is between 3 and 5, and even more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene and i is equal to 5, d) 0% to 3% of at least one crosslinking monomer, comprising at least two ethylenic unsaturations are selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurates, allylic ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

the total weight of monomers a), b), c) and d) being equal to 100%.

In a variant which is also preferred, these thickeners are obtained by a copolymerization process which does not involve the crosslinking monomer d).

A final object of the invention resides in the aqueous formulations containing the copolymers according to the invention, in particular in aqueous paint formulations, inks and varnishes, in paper formulations and in particular in paper coating coatings, in formulations for textile printing, for detergents, cosmetics, drilling muds, cement and ceramics.

These aqueous formulations are characterized in that they contain from 0.01% to 5% by dry weight of the copolymers according to the invention relative to the total weight of said aqueous formulations, and more preferably in that they contain 0.05% by weight. % to 3% by dry weight of the copolymers according to the invention relative to the total weight of said aqueous formulations.

The following examples illustrate the invention without, however, limiting its scope.

Example 1

This example relates to the preparation, according to the process according to the invention, of a substituted cumyl phenol compound according to the invention. Test No. 1

This test relates to the manufacture of a hydrophobic compound of the cumyl phenol substituted type, of formula (I):

where R denotes the radical resulting from the reaction between styrene and cumyl phenol, and i is equal to 5.

To do this, in a 2-liter reactor provided with mechanical stirring and conventional heating by an oil bath, the following are introduced:

636 grams of para-cumyl phenol, 11 grams of compound BF ₃ , 45 grams of toluene.

The medium is heated to 35 ^° C., and once this temperature is reached, 1565 grams of styrene are introduced for 6 hours by means of a peristaltic pump. Throughout the duration of the reaction, this time is maintained at a temperature of 45 ^° C.

Then, the reaction medium is distilled under vacuum in order to extract the toluene.

A viscous resin consisting of penta styryl cumyl phenol is then obtained. Example 2

This example relates to the use according to the invention, of a compound of formula (I) in a polymerization process, as it relates to the copolymers according to the invention thus obtained.

Test n ° 2

This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:

a) 43.5% of methacrylic acid b) 47.6% of ethyl acrylate c) 8.9% of a monomer of formula (II) where: - m = 0; n = 25; p = 0; q = 1;

R 'denotes the methacrylic ester;

- R "denotes the hydrophobic substituent of the hydrophobic compound of formula (I) obtained according to test No. 1.

Test n ° 3

a) 43.5% of methacrylic acid b) 47.6% of ethyl acrylate c) 8.9% of a monomer of formula (II) where:

- m = 0; n = 35; p = 0; q = 1;

R 'denotes the methacrylic ester; - R "denotes the hydrophobic substituent of the hydrophobic compound of formula (I) obtained according to test No. 1.

Test n ° 4 Test n ° 4

- m = 0; n = 50; p = 0; q = 1; R 'denotes the methacrylic ester;

Test n ° 5

a) 40.3% of methacrylic acid b) 54.6% of ethyl acrylate c) 5.1% of a monomer of formula (II) where:

- m = 0; n = 25; p = 0; q ≈ 1;

R 'denotes the methacrylic ester;

Test n ° 6

a) 40.3% methacrylic acid b) 54.6% ethyl acrylate c) 5.1% of a monomer of formula (II) where:

m = 0, n = 35, p = 0; q = l;

R 'denotes the methacrylic ester;

Test n ° 7

a) 40.3% of methacrylic acid b) 54.6% of ethyl acrylate c) 5.1% of a monomer of formula (II) where: - m = 0; n = 50; ; q = 1;

R 'is the methacrylic ester;

Test n ° 8

a) 37.2% methacrylic acid; (b) 52.8% ethyl acrylate; c) 10.0% of a monomer of formula (II) where:

m = 0, n = 25, p = 0; q = l;

- R 'denotes the methacrylic ester - R "denotes the hydrophobic substituent of the hydrophobic compound of formula (I) obtained according to test No. 1.

Test n ° 9 This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:

a) 37.2% of methacrylic acid b) 52.8% of ethyl acrylate c) 10.0% of a monomer of formula (II) where:

m = 0, n = 35, p = 0; q = 1;

R 'denotes the methacrylic ester

Test n ° 10

a) 37.2% of methacrylic acid b) 52.8% of ethyl acrylate c) 10.0% of a monomer of formula (II) where: - m ^≈ 0; n = 50; 0; q≈l;

R 'denotes the methacrylic ester;

Test n ° 11

a) 45.0% of methacrylic acid b) 43.0% of ethyl acrylate c) 12.0% of a monomer of formula (II) where:

- m ^≈ 0; n = 25; p = 0; q = l; R 'denotes the methacrylic ester;

Test n ° 12

- m = O; n = 35; p = O; q = 1;

Test n ° 13

- m = 0; n = 50; p = 0; q = 1;

R 'denotes the methacrylic ester;

Test n ° 14

This test relates to the manufacture of a copolymer according to the invention, the result of the copolymerization, expressed by weight, of:

a) 36.2% of methacrylic acid b) 53.9% of ethyl acrylate c) 9.9% of a monomer of formula (II) where:

- m = 0; n≈2S; p≈0; q = l;

R 'denotes the methacrylic ester;

Test n ° 15

m = 0, n = 35, p = 0; q = 1; R 'denotes the methacrylic ester;

Test n ° 16

m = 0, n = 50, ρ = 0, q = 1;

Tests Nos. 2 to 16 demonstrate that it is possible to obtain copolymers according to the invention containing a hydrophobic compound of formula (I) which, after ethoxylation and addition of ethylenic unsaturation, has 55 atoms. carbon: it was indeed one of the objectives hitherto never reached by the skilled person.

Example 3

This example relates to the use as thickeners of copolymers according to the invention and according to the prior art, in aqueous formulations containing water, a binder and said thickener.

To do this, we begin by preparing with stirring an aqueous formulation according to the following method.

In a beaker of 250 ml is introduced 176.7 grams of a binder which is Mowilith ™ DM123 (marketed by CELANESE ™) and 41.9 grams of bipermuted water.

This mixture is placed under mechanical stirring at 800 ± 50 rpm.

7.0 grams of the copolymer to be tested are then added, and the necessary amount of

NH ₄ OH (28%) to stabilize the pH between 9.0 and 9.5. During the following 3 minutes, the stirring is set at 1600 rpm and 2 drops of Nopco ™ NDW is introduced which is an antifoam agent marketed by the company COGNIS ™, and the necessary amount of NH ₄ is finally added. OH (to

28%) to stabilize the pH between 8.6 and 8.9.

The viscosity ICI ™ of the aqueous formulation obtained is then determined according to the method perfectly known to those skilled in the art on a cone-plane viscometer, said viscometer ICI ™, sold by the company ERICHSEN ™. The measurement is carried out at 25 ° C. and is marked μ ¹ (mPa.s). The Stormer ™ viscosity is determined on a Stormer viscometer type KU-I marketed by Brookfield ™, equipped with a single measurement system. The measurement is carried out at 25 ° C. and denoted μ ^s (KU).

Brookfield ™ viscosity is measured using a Brookfield ™ type RVT viscometer, in the unstirred bottle, at a temperature of 25 ° C and at a rate of 10 rpm with the appropriate rotor. Playback is performed after 1 minute of rotation. This gives a Brookfield ™ viscosity measurement noted μ ^B ₁₀ (mPa.s).

The values of these viscosities are indicated in Table 1, for the test 17 which illustrates the prior art, and which implements a copolymer of the prior art which is a HASE thickener having a hydrophobic group which has 30 carbon atoms.

The values of these viscosities are also indicated in Table 1, for tests 18 to 29 which illustrate the invention, implementing the copolymers corresponding to Tests 5 to 16 of Example 2, respectively.

Table 1: Viscosities of the aqueous formulations according to the invention at low, medium, and high shear rate. Reading Table 1 shows that the copolymers according to the invention, compared to the copolyraère of the prior art, very significantly improve the viscosities of the aqueous formulations containing them, for a low, medium or high shear gradient: these copolymers make it possible to obtain a compromise between good dynamic behavior and good static behavior, which was the objective of the person skilled in the art.

Example 4

This example relates to the use as thickeners of a copolymer of the prior art and novel copolymers according to the invention, in aqueous paint formulations.

The composition of said paints is shown in Table 2. The paints are formulated according to techniques well known to those skilled in the art.

Table 2: Composition of the paints according to the invention The ICI ™ viscosity of the paint formulation obtained is then determined on a cone-plane viscometer, called the ICI ™ viscometer, sold by the company ERICHSEN ™, according to the method that is well known to those skilled in the art. The measurement is carried out at 25 ^° C. and is marked μ ¹ (mPa.s).

The Stormer ™ viscosity is determined on a Stormer viscometer type KU-I marketed by Brookfield ™, equipped with a single measurement system. The measurement is carried out at 25 ° C. and denoted μ ^s (KU).

The Brookfield ™ viscosity is measured using a Brookfield ™ type RVT viscometer, in the unstirred bottle, at a temperature of 25 ^° C. and at a speed of 10 rpm with the appropriate rotor. Playback is performed after 1 minute of rotation. This gives a Brookfield ™ viscosity measurement noted μ ^B w (mPa.s).

The values of these viscosities are shown in Table 3, for the test which uses a prior art copolymer which is a HASE type thickener comprising a hydrophobic group which has 30 carbon atoms, as well as for the tests. 31 and 32, implementing the copolymers respectively corresponding to tests 10 and 16 of Example 2.

Table 3: Viscosities of aqueous paint formulations according to the invention and according to the prior art at low, medium, and high shear rate.

Reading from Table 3, it can be seen that the copolymers according to the invention significantly increase the viscosities of the aqueous formulations containing it relative to the formulation containing a thickener of the prior art, for a low, medium or high shear gradient. these copolymers make it possible to obtain a compromise between good dynamic behavior and good static behavior, which was the objective of the skilled person.

Example 5

This example relates to the use as thickeners of a copolymer of the prior art and novel copolymers according to the invention, in aqueous paint formulations (matte).

To do this, the same aqueous paint is produced as that corresponding to the composition described in Table 2 of Example 4.

This paint is introduced into a copolymer of the prior art which is the thickener of HASE type comprising a hydrophobic group with 30 carbon atoms, and used in test No. 30: this formulation corresponds to the test # 33.

A copolymer according to the invention which is the copolymer corresponding to test No. 16 is introduced into this paint: this formulation corresponds to test No. 34.

For the tests 33 and 34, the rheological profiles of the corresponding paints are carried out, ie the viscosity (mPa.s) is measured as a function of the shear gradient (s ^{' 1} ), on a device Haake RS 150 marketed by the company THERMORHEO ™. The corresponding rheological profiles are shown in FIG.

Figure 1: rheological profiles of the paints whose composition is given in Table 1, and containing a thickener of the prior art (- -) and a thickener according to the invention (-)

Reading Graph 1 demonstrates that the aqueous paint formulation containing a copolymer according to the invention has a higher viscosity than the aqueous formulation of ^p einture containing a copolymer of the prior art, regardless of the shear rate.

Example 6 This example relates to the preparation, according to the process according to the invention, of a substituted cumyl phenol compound according to the invention.

Test n ° 35

(i) where R denotes the radical resulting from the reaction between vinyl acetate and cumyl phenol, and i is equal to 5.

To do this, in a 1-liter reactor provided with mechanical stirring and conventional heating by an oil bath, the following are introduced:

197 grams of para-cumyl phenol, 3.4 grams of compound BF _3; 21.8 grams of toluene.

The medium is heated to 35 ° C., and once this temperature is reached, 400 grams of vinyl acetate are introduced for 6 hours, using a peristaltic pump. Throughout the duration of the reaction, the medium is maintained at a temperature of 30 ^° C.

Then, the reaction medium is distilled under vacuum in order to extract the toluene. A viscous resin is then obtained which contains the compound according to the invention as described at the beginning of test No. 35.

Example 7

Test n ° 36

(a) 37.15% methacrylic acid

(b) 52.8% ethyl acrylate

(c) 10.05% of a monomer of formula (II) where:

- m = 0; n = 25; p = 0; q = 1; R 'denotes the methacrylic ester;

Test n ° 37

(a) 36.2% methacrylic acid (b) 53.9% ethyl acrylate

(c) 9.9% of a monomer of formula (II) where:

- m = 0; n = 25; p = 0; q = 1;

Test n ° 38

(a) 37.2% methacrylic acid (b) 52.8% butyl acrylate

(c) 10.0% of a monomer of formula (II) where:

- m = 0; n = 25; p = 0; q = 1;

R 'denotes the methacrylic ester;

- R "refers to the hydrophobic substituent of the hydrophobic compound of formula (I) obtained according to test No. 1.

Test n ° 39

(a) 4.0% methacrylic acid

(b) 92.0% ethyl acrylate

(c) 4.0% of a monomer of formula (II) where: - m = 0; n = 25; p = 0; q = 1;

R 'denotes the methacrylic ester;

Test n ° 40

This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of: (a) 49.0% acrylic acid and 23.0% methacrylic acid

(b) 5.0% ethyl acrylate

(c) 23.0% of a monomer of formula (II) where:

- m = 0; n = 25; p = 0; q = 1;

R 'denotes the methacrylic ester;

Example 8

This example relates to the use as a thickener of a copolymer of the prior art and a copolymer according to the invention, in gypsum board joint paste formulations.

The following formulation is carried out by adding the constituents below, in the order of Table 4, with stirring in a planetary mixer. After mixing, the Brookfield ™ viscosity at 10 rpm of the formulation is measured at T = O (To) and T = 2400 (T ₂₄ ).

Test No. 41 illustrates the prior art and uses a copolymer of methacrylic acid and ethyl acrylate.

Test No. 42 illustrates the invention and uses the copolymer obtained for test No. 40.

Table 4: Composition of joint paste formulations for drywall.

The use of the copolymer according to the invention makes it possible to obtain, at T = 0, a Brookfield® viscosity measured at 10 rpm greater than that obtained with the polymer of the prior art, and a maintenance of this viscosity in the time.

Example 9

This example relates to the use as a thickener of a copolymer according to the invention, in a moisturizing formulation for the skin used in the field of cosmetics.

The formulation, the composition of which is given in Table 5, is carried out by mixing the following phases:

Table 5: Test No. 43 corresponding to a moisturizing skin composition composition according to the invention, using the copolymer according to the invention obtained in Test No. 38.

Test No. 43 illustrates the invention and uses the copolymer obtained in test No. 38 (formulation given in Table 5).

Test No. 43 bis is a control without thickener (formulation identical to that given in Table 5, but without thickener).

Phase B is added in phase A previously homogenized.

In parallel, phase C is homogenized by raising it to 70 ^° C. with stirring.

The homogenized A + B phases are brought to 70 ^° C. and mixed with the phase C. The mixture of the A + B + C phases is cooled with stirring of 70 ^° C. to 60 ^° C. and then, without stirring, from 60 ^° C. to 30 ^° C. ⁰ C.

Ià] pfiâs Ty ^ ^ ^ Fator ¥ àjôϋïé

30 ^° C.

The pH of the A + B + C + D phases is then adjusted to 6.8 with the E phase. The F phase is then added with stirring to the mixture of the A + B + C + D + E phases. The Brookfield ™ viscosities, for different rotational speeds, are measured 24 hours after the preparation at 25 ^° C., and are given in Table 6.

Table 6: Brookfield ™ viscosities, for different rotational speeds, measured 24 hours after the preparation, at 25 ° C, on moisturizing formulations for the skin according to the invention and without thickener.

Reading Table 6 demonstrates that the copolymer according to the invention makes it possible to thicken a moisturizing cream formulation.

Example 10

This example relates to the use as a thickener of a copolymer according to the invention, in a shampoo formulation in the field of cosmetics.

The shampooing formula is produced by mixing the following compounds with stirring, as indicated in Table 7. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is facilitated. .

Once the mixture is made, the Brookfield ™ viscosity is measured immediately (T ₀ ) and after 24:00 (T ₂₄ ), at different speeds.

Trial No. 44. illustrates the invention e_tmet. in order _. copolymer obtained according to test No. 37.

Test No. 45 is a control made without thickener.

Table 7: shampoo compositions according to the invention (using a copolymer according to the invention) and reference composition without thickener, and Brookfield ™ viscosities measured at different speeds of rotation and different times (T = 0 is To and T = 24 hours or T ₂₄ ).

The copolymer of the invention makes it possible to thicken a shampoo formula.

Example 11

This example relates to the use as a thickener of a copolymer according to the invention, in a scouring cream formulation in the field of detergency.

The scrubbing cream formulation is made by mixing the following compounds with stirring, as indicated in Table 8. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is is easier.

Test No. 46 illustrates the invention ^"rolled éh implement the copolymer obtained" by T test - # 36.

Test No. 47 is a control made without thickener. T / FR2005 / 002703

50

Once the mixture is made, the Brookfield ™ viscosity is measured at time T = O (To) for different rotational speeds; the corresponding values are given in Table 8.

Table 8: scouring cream compositions according to the invention (using a ¹ copolymer according to the invention) and control composition without thickener, and Brookfield ™ viscosities measured at different speeds of rotation and at T = 0 (T ₀ ).

The copolymer of the invention makes it possible to thicken a scouring cream formulation.

Example 12

This example relates to the use as a thickener of a copolymer according to the invention and a copolymer of the prior art, in a liquid soap formulation.

The washing formulations for the hands are more and more using liquid soaps of natural or synthetic origin. Unlike some surfactants, these Savo ^ή SLIE can ^"often not ^be thickened to-medium-d & ehlorure de sodium. To-des-economic reasons, they are often diluted and consequently lose all viscosity. To keep them Appearance consistent with use, a thickening agent should be used as described in the following tests. The formulation is carried out by stirring with the following compounds, as indicated in Table 9. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is facilitated.

Test No. 48 illustrates the prior art and uses a copolymer of methacrylic acid and ethyl acrylate.

Test No. 49 illustrates the invention and uses the copolymer obtained in test No. 38.

Once the mixture is completed, the soap is left standing for 24 hours and the Brookfield ™ viscosity is measured at 10 and 100 rpm.

Table 9: Liquid soap compositions according to the invention (using a copolymer according to the invention) and composition according to the prior art, and Brookfield ™ viscosities measured at different speeds of rotation and at T = 24 hours (T ₂₄ ).

The copolymer of the invention makes it possible to obtain a viscosity higher than the copolymer of the prior art.

Example 13

This example relates to the use of a copolymer according to the invention in alcoholic washing formulations.

Some washing formulations for the soil must be effective while not leaving no trace in the absence of rinsing. For this purpose, the formulator uses a mixture of water, alcohol and surfactant. This formulation should be slightly thickened so that it can be used with ease.

The formulation is carried out by stirring the following compounds, as indicated in Table 10. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is facilitated.

Test No. 50 illustrates the invention and uses the copolymer obtained in test No. 37.

Test No. 51 is a control made without thickener.

Once the mixture is made, the Brookfield ™ viscosity is measured at T = O (TQ).

Table 10: liquid soap compositions according to the invention (using a copolymer according to the invention) and control composition (without thickener), and Brookfield® viscosities measured at 10 revolutions / minute and at T = 0 (T ₀ ).

The copolymer of the invention makes it possible to thicken the alcohol-based formulation, thus making it easily usable.

Example 14 This example illustrates the use of a copolymer according to the invention in a textile printing paste.

The following formulation, the composition of which is given in Table 11, is used as the basis for textile printing pastes. Once thickened, this formulation is added with a pigment to then be applied to the tissues by all known methods, such as for example and without limitation, screen printing and rolls.

The printing paste formulation is carried out by mixing the following compounds with stirring, as indicated in Table 11. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula find it easier.

Test No. 52 illustrates the invention and uses the copolymer obtained in test No. 36.

Test No. 53 is a control made without thickener.

Once the mixture is made, the Brookfield viscosity is measured at different rotational speeds, and at time T = 0 (T ₀ ).

Table 11: Textile printing paste compositions according to the invention (using a copolymer according to the invention) and control composition (without thickener), and Brookfield ™ viscosities measured at different speeds and at T = O (T ₀ ). The copolymer of the invention makes it possible to significantly thicken the formulation.

Example 15

This example illustrates the use of a copolymer according to the invention in an enameling vehicle formulation used in the field of ceramics.

The following formulation is called an enameling vehicle because it is used as a vector for remeshing ceramics such as, and not limited to, tiles and sanitary parts. This formulation will be used as a liquid in which powdered enamels will be dispersed and eventually crushed. The addition of a thickener provides a satisfactory final viscosity for easy application and stabilization of the enamel dispersion storage.

The enameling vehicle formulation is carried out by mixing the following compounds with stirring, as indicated in Table 12. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula find it easier.

Test No. 54 illustrates the invention and uses the copolymer obtained in test No. 36.

Test No. 55 is a control made without thickener.

Once the mixture is made, the viscosity of the formulation is measured using a Ford ™ cup equipped with a 4 mm orifice.

Table 12: Enameling vehicle compositions according to the invention (using a copolymer according to the invention) and control composition (without thickener), and Ford ™ cutting viscosities with a diameter of 4 mm thus obtained.

The copolymer of the invention makes it possible to increase the viscosity of the enameling vehicle formulation.

Example 16

This example illustrates the use of a copolymer according to the invention and a copolymer of the prior art in a slip formulation, used in the field of ceramics.

The manufacture of ceramic parts and materials involves the use of dispersions of clays and various minerals milled in aqueous phase. In the case of some parts, the ground dispersion of these minerals, called slip, can be kept in liquid form for use by molding or casting. While some applications require a slip of low viscosity, others require a higher viscosity to either maintain the particles of minerals in suspension, or to give the slip characteristics of viscosity allowing its application by casting in mold or strip . For this purpose, a thickener in aqueous phase can be used as described in the following tests.

The slip formulation is produced by mixing the following compounds with stirring, as indicated in Table 13. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is facilitated.

Test No. 56 illustrates the prior art and employs a copolymer of methacrylic acid and ethyl acrylate.

Test No. 57 illustrates the invention and uses the copolymer obtained in test No. 36. Once the mixture is made, the Brookfield ™ viscosity of the formulation is measured at time T = O (T ₀ ).

Table 13: slip compositions according to the invention (using a copolymer according to the invention) and composition of the prior art (with a thickener of the prior art), and Brookfield ™ viscosities measured at different speeds and at T = 0 (TB).

The copolymer of the invention makes it possible to obtain a higher viscosity than the polymer of the prior art.

Example 17

This example illustrates the use of a copolymer according to the invention and a copolymer of the prior art in a finishing formulation used in the field of leathers.

Leather (leather) items often need to be covered with a protective film to ensure a uniform appearance and / or water resistance. This protection can be achieved by the application of a varnish in aqueous phase. The formulation below exemplifies the use of the copolymer of the invention in order to thicken a formulation based on an acrylic emulsion in aqueous phase, thickening necessary for easy application by any known means of the formulator. Indeed, this non-thickened formulation has a very low viscosity resulting in sagging during the application of the varnish if the latter is not thickened. The coating formulation is carried out by stirring the following compounds, as indicated in Table 14. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is facilitated. .

Test No. 58 illustrates the prior art and uses a copolymer of methacrylic acid and ethyl acrylate.

Test No. 59 illustrates the invention and uses the copolymer obtained in test No. 37.

Once the formulation is made, the Brookfield ™ viscosity is measured to verify the thickening effect of the products, at time T = O (TB).

Table 14: Composition of a finishing formulation in the field of leather, according to the invention (using a copolymer according to the invention) and composition of the prior art (with a thickener of the prior art), and Brookfield viscosities ™ measured at different speeds and at T = O (To).

The copolymer of the invention makes it possible to obtain a viscosity higher than the polymer of the prior art.

Example 18 This example illustrates the use of a copolymer according to the invention and a copolymer of the prior art in the formulation of a fat emulsion used in the treatment of leathers.

A large number of fat emulsions are used in the treatment of hides and skins in order to bring to the finished product, among others but without limitation, characteristics of flexibility and water resistance. These emulsions consisting of animal, vegetable or synthetic oils can be transported over long distances or stored for extended periods. Then there is the problem of their stability, a problem that can be partially solved by increasing their active ingredient content. However, this increase must often be important in order to obtain a stable emulsion and generally results in a very high viscosity making handling of the product difficult. The use of a thickening polymer overcomes this disadvantage by providing a high viscosity at rest but decreasing rapidly during the handling of the emulsion, thereby obtaining a stable product but easily manipulated. The tests below highlight the property of the copolymer of the invention to fulfill this function.

Stabilization of the emulsion is carried out by stirring the following compounds, as indicated in Table 15. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is is easier.

Test No. 60 illustrates the prior art and uses a copolymer of methacrylic acid and ethyl acrylate.

Test No. 61 illustrates the invention and uses the copolymer obtained in test No. 38.

Once the formulation is made, the Brookfield ™ viscosity is measured at T = 0 (TB) at 10 and 100 rpm to verify the thickening effect of the products.

Table 15: fat emulsion composition used in the treatment of leather, according to the invention (using a copolymer according to the invention) and composition of the prior art (with a thickener of the prior art), and Brookfield® viscosities measured at different speeds and at T = O (To).

The copolymer of the invention makes it possible to obtain a higher viscosity than the polymer of the prior art while increasing the ratio between the viscosities measured at 10 and 100 revolutions / minute, resulting in a viscosity measured at 10 revolutions / minute identical to by greater stability at rest, with easier handling due to a viscosity measured at 100 rpm lower.

Example 19

This example illustrates the use of a copolymer according to the invention in a cement dispersion used in the cementation of the wellbore.

When drilling wells for oil or other materials such as water or gas, it will be necessary to consolidate the walls of the well when it must enter into operation or during drilling if the need 'actually feel. For this purpose, it is commonly used aqueous dispersions of cement whose simplest composition is based on water, thickeners, dispersant and cement. Other products may be used such as weighting agents (barite, hematite) or other additives such as foaming agents or filtrate reducers. The formulation below is therefore in no way limiting. The cement dispersion is carried out by mixing the following compounds with stirring, as indicated in Table 16. The order of introduction is not fundamental, but respecting the chronology, the manufacture of the formula is facilitated. .

Test No. 62 illustrates the invention and uses the copolymer obtained in test No. 36.

Test No. 63 is a control made without thickener.

Once the dispersion is carried out, the viscosity is measured by means of a Ford ™ cup with a diameter of 4 mm in order to verify the thickening effect of the polymer of the invention.

Table 16: Composition of a cement dispersion according to the invention (using a copolymer according to the invention) and control composition (without thickener), and values of Ford ™ cutting viscosities with a corresponding diameter of 4 mm.

A low dose of the copolymer of the invention makes it possible to thicken the dispersion.

Example 20

This example illustrates the use of a copolymer according to the invention in a mortar formulation.

When using hydraulic binders, as desired, the processor may be required to manufacture a cementitious composition whose viscosity must be increased in order to promote the holding of the mixture during application or at a later date. early release. This application is of course in no way limiting and the polymer of the invention may be used whenever a thickening is necessary in a cementitious composition or hydraulic binder, for any application whatsoever.

The manufacture of this mortar is carried out in a mortar mixer by mixing the following compounds with stirring, as indicated in Table 17. The order of introduction is not fundamental, but respecting the chronology and the times addition, the manufacture of the formula is facilitated.

Test No. 64 illustrates the invention and uses the copolymer obtained in test No. 37.

Test No. 65 is a control made without thickener.

Once the formula is manufactured, the viscosity is measured by means of a shock table in order to verify the thickening effect of the copolymer of the invention. This thickening results in a reduced spread of the mortar slab on the impact table.

Table 17: mortar composition according to the invention (containing a copolymer according to the invention) and control composition (without thickener), and values of the viscosities measured from-table-to-ehθ67

The copolymer of the invention makes it possible to substantially reduce the spreading of the mortar, which reflects an increase in viscosity. Example 21

This example illustrates the use of a copolymer according to the invention in a plaster formulation.

Plaster of Paris (calcium sulphate, hemihydrate) is very often used in binding, sticking or jointing compositions for construction. It can be combined with other mineral fillers or not. Some uses require the dispersion to have a certain viscosity to facilitate its implementation.

The following formulation, as indicated in Table 18, is composed of plaster of Paris and calcium carbonate. Its viscosity is controlled by means of a Schmidt ™ ring with an inside diameter of 6 cm. This ring is placed on a glass plate, filled with the formulation and raised with a fast and regular movement. The plaster dispersion then spreads into a wafer of a diameter proportional to its viscosity. In this case, one seeks a zero spread, the dispersion although manipulable must remain motionless. Used for example in grouting, this formulation will remain in place without deforming after its application.

The formulation below is carried out by stirring the following compounds. The order of introduction is not fundamental but respecting the chronology, the manufacture of the formula is facilitated.

Test No. 66 illustrates the prior art and uses a copolymer of methacrylic acid and ethyl acrylate.

Test No. 67 illustrates the invention and uses the copolymer obtained in test No. 37.

Table 18: plaster composition according to the invention (containing a copolymer according to the invention) and composition of the prior art (with a copolymer of the prior art), and corresponding spreading values as measured with a ring of Schmidt ™.

The copolymer of the invention makes it possible to reduce the spreading of the plaster, which indicates an increase in viscosity.

Example 22

This example illustrates the use of copolymers according to the invention and a copolymer of the prior art in a bentonite formulation based on freshwater or seawater.

When drilling a well for the purpose of looking for oil, gas or water, it uses among other drilling fluid whose purpose is to cool the drill bit and up the cuttings. This drilling fluid is very often water-based, soft or saline, and contains various mineral fillers for the purpose of giving it a certain consistency and a certain density. This sludge must have very well controlled viscosity characteristics in order to be able to easily remount the cuttings while _res_tant_pompab_le. The use of a thickening polymer makes it possible to finely adjust this viscosity to meet the specifications defined at the drilling site and depending on the type of rock formation traversed. The drilling muds below are made by stirring at high speed in a Hamilton mixer Beach of the following compounds. The order of introduction is not fundamental but respecting the chronology and the times of addition, the manufacture of the formula is facilitated.

Synthetic seawater is produced by dissolving in a final volume of one liter of the following salts:

Sodium chloride 44.05 g. Potassium chloride 0.67 g.

Calcium chloride dihydrate 1.36 g.

Magnesium Chloride Hexahydrate 4.66 g.

Magnesium sulphate heptahydrate 6.29 g.

Sodium hydrogen carbonate 0.18 g.

Test No. 68 is a control test in fresh water, without thickener.

Test No. 69 illustrates the prior art in freshwater, and uses a copolymer of methacrylic acid and ethyl acrylate.

Test No. 70 illustrates the invention in fresh water, and uses the copolymer obtained in test No. 37.

Test No. 71 is a control test in synthetic seawater, without thickener.

Test No. 72 illustrates the invention in synthetic seawater, and uses the copolymer obtained in test No. 38.

After preparation of the sludge, their ^{"cafâctéπstiquês} rheological ^{^} ^~ are measured-by means of a rheometer Fann ™. The use of thickening polymer is to increase the value of the measured viscosities.

Table 19: compositions based soft cTeau ^"ei ^{^'e'} to ^the" sea of synmëtique ^~ according to the invention (with a copolymer according to the invention), according to the prior art (with a thickener of the prior art) and control composition (without thickener), and measured Fann ™ viscosity values. The copolymer of the invention makes it possible to obtain a higher viscosity than the polymer of the prior art. This is particularly visible on the measurement at 0.3 rpm after 10 minutes of rest, which represents the capacity of the sludge to keep the cuttings in suspension during a shutdown of the sludge circulation pumps. A high value of this measurement is necessary to avoid any sedimentation of the cuttings at the bottom of the well, sedimentation which would cause a blockage of the drilling.

Example 23

This example illustrates the use of copolymers according to the invention in a varnish formulation.

The composition of said varnish is given in Table 20.

Test No. 73 is a control test without thickener.

Test No. 74 illustrates the invention and uses the copolymer obtained in test No. 36.

Test No. 75 illustrates the invention and uses the copolymer obtained in test No. 37.

Test No. 16 illustrates the invention and uses the copolymer obtained in test No. 38.

Test No. 77 illustrates the invention and uses the copolymer obtained in Test No. 40.

For each formulation, Brookfield ™ viscosities at 10 and 100 rpm, as well as Stormer ™ and ICI ™ viscosities are measured at T = 0, and according to methods well known to those skilled in the art.

Table 20: Varnish compositions and Brookfield ™ viscosity values (10 and 100 rpm), Stormer ™, ICI ™, measured at time T = O

The results in Table 20 demonstrate that the copolymers according to the invention make it possible to thicken a varnish.

Example 24

This example illustrates the use of a copolymer according to the invention in a coating of coating color formulation.

The composition of said coating color is given in Table 21; it is actually a formulation used for precoating paper. Test N ⁰ 78

This test is a control without thickener and implements 100 parts by weight of calcium carbonate marketed by the company OMYA ™ under the name Hydrocarb ™ 60 and 12 parts of an acrylic binder sold by the company DOW ™ under the name DL 966.

Brookfield ™ viscosity values, measured at time T = 0 at 10 and 100 rpm, are respectively 1030 mPa.s and 210 mPa.s.

Test No. 79

This test corresponds to the invention and uses 100 parts by weight of calcium carbonate marketed by OMYA ™ under the name Hydrocarb ™ 60, 12 parts of an acrylic binder marketed by DOW ™ under the name DL 966 and 0.3 parts by weight of the copolymer according to the invention obtained in test No. 36. The Brookfield ™ viscosity values, measured at time T = 0 at 10 and 100 rpm are respectively equal to 11,920 mPa.s and 2,960 mPa.s.

These results demonstrate that the copolymer according to the invention makes it possible to advantageously thicken a paper coating sauce.

Claims

1 - Hydrophobic compounds of the substituted cumyl phenols type, characterized in that they have the formula (I):

and i denotes an integer between 1 and 5.

2 - Hydrophobic compounds according to claim 1, characterized in that R denotes the radical resulting from the reaction between cumyl phenol and an alkene selected from styrene, octadecene and vinyl acetate and their mixtures and i is between 1 and 5.

3 - Hydrophobic compounds according to claim 2, characterized in that R denotes the radical resulting from the reaction between cumyl phenol and an alkene selected from styrene, octadecene, vinyl acetate and mixtures thereof, and i is included between 3 and 5.

4 - Hydrophobic compounds according to claim 3, characterized in that R denotes the radical resulting from the reaction between cumyl phenol and styrene, and i is equal to 5.

5 - Process for synthesizing compounds of formula (I)

where R denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes, and i denotes an integer between 1 and 5,

characterized in that it is an alkylation reaction of cumyl phenol, involving cumyl phenol and an alkene or a mixture of alkenes.

6 - synthesis process according to claim 5, characterized in that R denotes the radical resulting from the reaction between cumyl phenol and an alkene selected from styrene, octadecene, vinyl acetate and mixtures thereof and i is included between 1 and 5.

7 - synthesis process according to claim 6, characterized in that R denotes the radical resulting from the reaction between cumyl phenol and an alkene selected from styrene, octadecene, vinyl acetate and mixtures thereof, and i is between 3 and 5.

8 - Synthesis process according to claim 7, characterized in that R denotes the radical resulting from the reaction between cumyl phenol and styrene, and i is equal to 5.

9 - Synthesis process according to one of claims 5 to 8, characterized in that the synthesis temperature is between 25 ° C and 50 ° C, in that the catalyst is a Lewis acid and preferably the compound of formula BF ₃ , and in that the synthesis solvent is an aromatic solvent and preferably toluene. Use of compounds of formula (I)

(I) wherein R denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes, and i denotes an integer between 1 and 5,

in a polymerization process, characterized in that the following are copolymerized:

b) at least one ethylenically unsaturated nonionic monomer,

11 - Use in a copolymerization process of compounds of formula (I), according to claim 10, characterized in that:

a) the monomer (s) with ethylenic unsaturation and with a carboxylic function are chosen from monomers with ethylenic unsaturation and monocarboxylic functional groups such as acrylic or methacrylic acid, or else diacid hemiesters such as C ₁ -C ₄ monoesters of maleic or itaconic acids, or mixtures thereof, or selected from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or still furthermore the anhydrides of carboxylic acids, such as maleic anhydride, and more preferentially in that the monomer with ethylenic unsaturation and with a carboxylic function is methacrylic acid,

(H) wherein: m and p represent a number of alkylene oxide units ranging from 0 to 150,

n represents a number of ethylene oxide units ranging from 5 to 150; q represents an integer at least equal to 1 and such that 5 <(m + n + p) q <150, and preferentially such that <(m + n + p) q <120, R ₁ represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

R 'represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, and also to the group of urethane unsaturates such as acrylurethanes and methacrylurethanes; α-α 'dimethyl-isopropenyl-benzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or alternatively to the group of ethylenically unsaturated amides or imides, R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5, more preferably where R denotes the radical resulting from the reaction. between cumyl phenol and an alkene selected from styrene, vinyl acetate, octadecene and mixtures thereof and is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene, vinyl acetate, octadecene and their mixtures and i is between 3 and 5, and even more preferentially where R denotes the radical resulting from the reaction between cumyl phenol and styrene and i is equal to 5,

d) the optional monomer or monomers, referred to as crosslinking monomers, comprising at least two ethylenic unsaturations are chosen from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, acrylate allyl, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allyl ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

12 - Use in a copolymerization process of compounds of formula (I), according to one of claims 10 or 11, characterized in that the copolymer thus produced is the result of the copolymerization, expressed by weight of the monomers, of: a) 2 to 95%, and preferably 5 to 90% of at least one ethylenically unsaturated monomer containing a carboxylic function chosen from monomers containing ethylenic unsaturation and monocarboxylic functional groups, such as acrylic or methacrylic acid, or even diacid hemiesters such as the C ₁ -C ₄ monoesters of maleic or itaconic acids, or mixtures thereof, or selected from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride, and more preferably from 2 to 95%, and preferably from 5 to 90% of methacrylic acid,

(H) wherein: m and p represent a number of alkylene oxide units ranging from 0 to 150, n represents a number of ethylene oxide units ranging from 5 to 150,

q represents an integer at least equal to 1 and such that 5 <(m + n + p) q <150, and preferentially such that <<(m + n + p) q <120,

0% to 3% of at least one crosslinking monomer comprising at least two ethylenic unsaturations are chosen from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, acrylate allyl, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurate, allyl ethers obtained ^'from polyols selected from pentaerythritol, sorbitol, or sucrose.

the total weight of monomers a), b), c) and d) being equal to 100%.

13 - Use in a copolymerization process of compounds of formula (I), according to one of claims 10 to 12, characterized in that the copolymerization process is a direct emulsion process, or inverse, or in solution, or by precipitation.

14 - Copolymers characterized in that they are the result of the copolymerization:

b) at least one ethylenically unsaturated nonionic monomer,

c) at least one ethylenically unsaturated oxyalkylated monomer, constituted by the result of the ethoxylation of a hydrophobic compound of formula (I), made polymerizable by adding an ethylenic unsaturation,

15 - Copolymers according to claim 14, characterized in that:

a) the ethylenically unsaturated monomer (s) containing a carboxylic function are chosen from ethylenically unsaturated and monocarboxylic functional monomers such as acrylic or methacrylic acid, or also diacid semiesters such as C ₁ -C ₄ monoesters; maleic or itaconic acids, or mixtures thereof, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as anhydride. maleic, and more preferably in that the monomer with ethylenic unsaturation and with a carboxylic function is methacrylic acid,

150, n represents a number of ethylene oxide units ranging from 5 h 150, q represents an integer at least equal to 1 and such that 5 <(m + n + ρ) q <

150, and preferentially such that <(m + n + p) q <120,

R 1 represents the methyl or ethyl radical,

R2-represents methyl radical or _. ethyl,

R 'represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters; as well as to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α-dimethylisopropenyl-benzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else to the group of amides or ethylenically unsaturated imides,

R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5; , more preferably where R denotes the radical resulting from the reaction between cumyl phenol and an alkene chosen from styrene, vinyl acetate, octadecene and their mixtures and i is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene, vinyl acetate, octadecene and their mixtures and is between 3 and 5, and even more preferably where R denotes the radical resulting from the reaction between the cumyl phenol and styrene and i is equal to 5,

d) the optional monomer or monomers, called crosslinking monomers, comprising at least two ethylenic unsaturations are chosen from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allylic ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

16 - Copolymers according to one of claims 15 or 16, characterized in that they are the result of the copolymerization, expressed by weight of the monomers, of:

a) from 2% to 95%, and preferably from 5% to 90%, of at least one ethylenically unsaturated monomer containing a carboxylic function chosen from monomers containing ethylenic unsaturation and monocarboxylic functional groups, such as acrylic or methacrylic acid, or still hemiesters of diacids such as C 1 to C ₄ monoesters of maleic or itaconic acids, or their mixtures, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride, and more preferably from 2 to 95%, and preferably 5 to 90% methacrylic acid,

- Λj: this is a number of ethylene oxide numbers ranging from 5 to L5i), q represents an integer at least equal to 1 and such that <<(m + n + p) q <150, and preferably such that <(m + n + p) q <120, R ₁ represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical,

R 'represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters as well as to the group of urethane unsaturates such as acrylurethanes and methacrylurethanes; α-α 'dimethyl-isopropenyl-benzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or alternatively to the group of ethylenically unsaturated amides or imides, - R "represents the hydrophobic substituent of the hydrophobic compound of formula (I), where R preferably denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes and i denotes an integer between 1 and 5, more preferably where R denotes the radical derived from the reaction between cumyl phenol and an alkene selected from styrene, vinyl acetate, octadecene and mixtures thereof and i is between 1 and 5, more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene, vinyl acetate, octadecene and their mixtures and i is between 3 and 5, and more preferably where R denotes the radical resulting from the reaction between cumyl phenol and styrene and i is equal to 5,

the total weight of monomers a), b), c) and d) being equal to 100%.

17 - Copolymers according to one of claims 14 to 16, characterized in that they are the result of a copolymerization process not involving the monomer crosslinking agent d).

18 - Use of the copolymers according to one of claims 14 to 17, as thickeners in aqueous formulations.

19 - Use of the copolymers according to claim 18 as thickeners in aqueous paints.

20 - Use of the copolymers according to claim 18 as thickeners in inks.

21 - Use of the copolymers according to claim 18, as thickeners in varnishes.

22 - Use of the copolymers according to claim 18, as thickeners in paper and preferably in paper coating coatings.

23 - Use of the copolymers according to claim 18 as thickeners in textile printing formulations.

24 - Use of the copolymers according to claim 18 as thickeners in detergent formulations.

Use of the copolymers according to claim 18 as thickeners in cosmetic formulations.

26 - Use of the copolymers according to claim 18 as thickeners in drilling muds.

27 - Use of the copolymers according to claim 18 as thickeners in cement formulations.

28 - Use of the copolymers according to claim 18, as thickeners in ceramic formulations.

29 - Use of the copolymers according to one of claims 18 to 28, characterized in that it implements from 0.01% to 5% by dry weight of the copolymers according to the invention relative to the total weight of said aqueous formulations and more preferably in that 0.05% to 3% by dry weight of the copolymers according to the invention are used relative to the total weight of said aqueous formulations.

Thickeners characterized in that they are the result of the copolymerization:

b) at least one ethylenically unsaturated nonionic monomer,

31 - Thickeners according to claim 30, characterized in that:

c) the ethylenically unsaturated oxyalkylated monomer or monomers constituted by the result of the ethoxylation of a hydrophobic compound of formula (I) rendered polymerizable by the addition of an ethylenic unsaturation, have the following formula (II):

(H)

wherein: m and p represent a number of alkylene oxide units ranging from 0 to

150, n represents a number of ethylene oxide units ranging from 5 to 150, q represents an integer at least equal to 1 and such that 5 ≤ (m + n + p) q <

150, and preferentially such that <(m + n + p) q <120,

R 1 represents the methyl or ethyl radical,

R ₂ represents the methyl or ethyl radical,

R 'represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters; as well as to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α-dimethylsulfenyl-benzylurethane, allylurethane, as well as to the group of substituted or unsubstituted allylic or vinyl ethers, or else to the group of ethylenically amide or imides. unsaturated,

32 - Thickeners according to one of claims 30 or 31, characterized in that they are the result of the copolymerization, expressed by weight of the monomers, of:

a) from 2% to 95%, and preferably from 5% to 90%, of at least one ethylenically unsaturated monomer containing a carboxylic function chosen from monomers containing ethylenic unsaturation and monocarboxylic functional groups, such as acrylic or methacrylic acid, or also the diacid hemiesters such as the C ₁ to C ₄ monoesters of maleic or itaconic acids, or their mixtures, or chosen from ethylenically unsaturated monomers and dicarboxylic functional groups such as crotonic acid, isocotonic acid, cinnamic acid, itaconic acid, maleic acid, or carboxylic acid anhydrides, such as maleic anhydride, and more preferably from 2 to 4 carbon atoms. at 95%, and preferably from 5 to 90% of methacrylic acid,

b) 2% to 95%, and preferably 5% to 90% of at least one ethylenically unsaturated nonionic monomer are chosen from esters, amides or nitriles of acrylic and methacrylic acids, such as acrylates or methacrylates methyl, ethyl, butyl, 2-ethyl-hexyl, or among racrylonitrile, vinyl acetate, styrene, methylstyrene, diisobutylene, vinylpyrrolidone, vinylcaprolactam, and more preferably from 2 to 95%, and preferentially from 5 to 90% of ethyl acrylate,

(H) wherein: m and p represent a number of alkylene oxide units ranging from 0 to 150, n represents a number of ethylene oxide units ranging from 5 to 150, -q-represents-a - integer-at least equal to 1-and such that -5 - <- (m + n + p) q - <- 150, and preferentially such that <<(m + n + p) q <120, Ri represents the methyl or ethyl radical, R ₂ represents the methyl or ethyl radical, R 'represents a radical containing a polymerizable unsaturated functional group, belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, as well as to the group of unsaturated urethanes such as acrylurethanes, methacrylurethane, α α-dimethylisopropenyl-benzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,

d) 0% to 3% of at least one crosslinking monomer containing at least two ethylenic unsaturations are selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, trimethylolpropane trimethacrylate, acrylate allyl, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, allylic ethers obtained from polyols chosen from pentaerythritol, sorbitol or sucrose.

the total weight of monomers a), b), c) and d) being equal to 100%.

33 - Thickeners according to one of claims 30 to 32, characterized in that said thickeners are obtained from a copolymerization process not involving the crosslinking monomer d). 34 - Aqueous formulations, characterized in that they contain the copolymer according to one of claims 14 to 17.

Aqueous formulations according to claim 34, characterized in that they are aqueous paint formulations.

36 - Aqueous formulations according to claim 34, characterized in that they are ink formulations.

37 - Aqueous formulations according to claim 34, characterized in that they are varnish formulations.

38 - Aqueous formulations according to claim 34, characterized in that they are paper formulations and preferably formulations of paper coating coatings.

39 - Aqueous formulations according to claim 34, characterized in that they are textile printing formulations.

40 - Aqueous formulations according to claim 34, characterized in that they are detergent formulations.

41 - Aqueous formulations according to claim 34, characterized in that they are cosmetic formulations.

42 - aqueous formulations according to claim 34, characterized in that they are formulations of drilling muds.

43 - Aqueous formulations according to claim 34, characterized in that they are cement formulations.

44 - Aqueous formulations according to claim 34, characterized in that they are ceramic formulations. 45 - Aqueous formulations according to one of claims 34 to 44, characterized in that they contain from 0.01% to 5% by dry weight of the copolymers according to the invention relative to the total weight of said aqueous formulations, and more preferably in that they contain from 0.05% to 3% by dry weight of the copolymers according to the invention relative to the total weight of said aqueous formulations.