Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
  • C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate

Definitions

• 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.
• HASE type Hydrodrophobically modified and alkaline-thickening modified emulsions or Hydrophobically modified Alkali-Soluble Emulsions
• the invention firstly relates to novel hydrophobic compounds of the substituted cumyl phenols type, of general formula (I):
• R denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes
• 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.
• the stress is a measure of the pressure applied to the aqueous formulation.
• the viscosities at low, medium, and high shear rate will be measured in the present application respectively through the Brookfield TM 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.
• 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.
• 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).
• HEUR type Ethylene oxide modified ethylene oxide or Hydrophobically modified ethylene oxide URethane
• HMHEC hydrophobically modified Hydroxyethylcellulose or Hydrophobically Modified Hydroxyethylcellulose
• HASE Hydrodrophobically 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 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.
• 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.
• 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.
• tristyrylphenol which has 30 carbon atoms.
• 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.
• a Lewis acid which is preferably the compound of formula BF 3
• solvents such as aromatic solvents and preferably toluene.
• 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.
• novel hydrophobic compounds of the cumyl phenols substituted type according to the invention are therefore obtained by an alkylation reaction of cumyl phenol.
• This 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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 ⁇ m 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):
• R denotes the radical resulting from the reaction between cumyl phenol and an alkene or a mixture of alkenes
• i denotes an integer between 1 and 5.
• 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.
• 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.
• 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.
• 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.
• R denotes the radical resulting from the reaction between cumyl phenol and styrene, and i is equal to 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:
• crosslinking monomer comprising at least two ethylenic unsaturations.
• 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,
• 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,
• n 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 + ⁇ ) 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, ⁇ ⁇ -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
• 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,
• n a number of ethylene oxide units ranging from 5 to 150
• q an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇
• 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, ⁇ ⁇ -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 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,
• 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.
• 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:
• crosslinking monomer comprising at least two ethylenic unsaturations.
• 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,
• 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,
• 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 acrylurethanes, methacrylurethane, ⁇ ⁇ -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,
• 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:
• 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
• n and p represent a number of alkylene oxide units ranging from 0 to 150
• n 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 ⁇
• 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; ⁇ - ⁇ -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,
• 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,
• 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.
• 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:
• thickeners are also characterized in that:
• 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,
• 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,
• m and p represent a number of alkylene oxide units ranging from 0 to 150
• n 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 + ⁇ ) 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; ⁇ - ⁇ -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,
• 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,
• 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.
• 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,
• n 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 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, ⁇ ⁇ -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 tyfèrie, T ' ac ⁇ fâtè ⁇ 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
• 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.
• 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.
• 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
• R denotes the radical resulting from the reaction between styrene and cumyl phenol, and i is equal to 5.
• 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.
• reaction medium is distilled under vacuum in order to extract the toluene.
• 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.
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R ' is the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• 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:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, the result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• 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.
• 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.
• This mixture is placed under mechanical stirring at 800 ⁇ 50 rpm.
• the viscosity ICI TM 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 TM, sold by the company ERICHSEN TM. The measurement is carried out at 25 ° C. and is marked ⁇ 1 (mPa.s).
• the Stormer TM viscosity is determined on a Stormer viscometer type KU-I marketed by Brookfield TM, equipped with a single measurement system. The measurement is carried out at 25 ° C. and denoted ⁇ s (KU).
• Brookfield TM viscosity is measured using a Brookfield TM 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 TM viscosity measurement noted ⁇ B 10 (mPa.s).
• 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.
• 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.
• 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 TM viscosity of the paint formulation obtained is then determined on a cone-plane viscometer, called the ICI TM viscometer, sold by the company ERICHSEN TM, 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 ⁇ 1 (mPa.s).
• the Stormer TM viscosity is determined on a Stormer viscometer type KU-I marketed by Brookfield TM, equipped with a single measurement system. The measurement is carried out at 25 ° C. and denoted ⁇ s (KU).
• Brookfield TM viscosity is measured using a Brookfield TM 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 TM viscosity measurement noted ⁇ B w (mPa.s).
• Table 3 Viscosities of aqueous paint formulations according to the invention and according to the prior art at low, medium, and high shear rate.
• 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.
• 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).
• 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.
• 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 TM.
• 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.
• R denotes the radical resulting from the reaction between vinyl acetate and cumyl phenol, and i is equal to 5.
• 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.
• 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.
• 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.
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• This test relates to the manufacture of a copolymer according to the invention, a result of the copolymerization, expressed by weight, of:
• R 'de notes the methacrylic ester
• 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
• R 'de notes the methacrylic ester
• 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.
• 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.
• 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 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.
• 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.
• 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 TM viscosities, for different rotational speeds, are measured 24 hours after the preparation at 25 ° C., and are given in Table 6.
• Table 6 Brookfield TM 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.
• 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. .
• 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.
• the copolymer of the invention makes it possible to thicken a shampoo formula.
• 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.
• the copolymer of the invention makes it possible to thicken a scouring cream formulation.
• 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 ⁇ 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.
• the soap is left standing for 24 hours and the Brookfield TM viscosity is measured at 10 and 100 rpm.
• the copolymer of the invention makes it possible to obtain a viscosity higher than the copolymer of the prior art.
• This example relates to the use of a copolymer according to the invention in alcoholic washing formulations.
• washing formulations for the soil must be effective while not leaving no trace in the absence of rinsing.
• 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.
• 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 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.
• the copolymer of the invention makes it possible to significantly thicken the formulation.
• 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.
• the viscosity of the formulation is measured using a Ford TM 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 TM 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.
• 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.
• the ground dispersion of these minerals called slip
• 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 .
• 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.
• the copolymer of the invention makes it possible to obtain a higher viscosity than the polymer of the prior art.
• 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.
• 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.
• 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.
• 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.
• This example illustrates the use of a copolymer according to the invention in a cement dispersion used in the cementation of the wellbore.
• 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.
• the viscosity is measured by means of a Ford TM 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 TM 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.
• This example illustrates the use of a copolymer according to the invention in a mortar formulation.
• 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.
• 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.
• 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-eh ⁇ 67
• the copolymer of the invention makes it possible to substantially reduce the spreading of the mortar, which reflects an increase in viscosity.
• 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 is composed of plaster of Paris and calcium carbonate. Its viscosity is controlled by means of a Schmidt TM 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 TM.
• the copolymer of the invention makes it possible to reduce the spreading of the plaster, which indicates an increase in viscosity.
• 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.
• 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:
• 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.
• Table 19 compositions based soft cTeau "ei 'e' to the" sea of synm ⁇ tique ⁇ 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 TM 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.
• This example illustrates the use of copolymers according to the invention in a varnish formulation.
• 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.
• This example illustrates the use of a copolymer according to the invention in a coating of coating color formulation.
• composition of said coating color is given in Table 21; it is actually a formulation used for precoating paper.
• This test is a control without thickener and implements 100 parts by weight of calcium carbonate marketed by the company OMYA TM under the name Hydrocarb TM 60 and 12 parts of an acrylic binder sold by the company DOW TM under the name DL 966.
• This test corresponds to the invention and uses 100 parts by weight of calcium carbonate marketed by OMYA TM under the name Hydrocarb TM 60, 12 parts of an acrylic binder marketed by DOW TM under the name DL 966 and 0.3 parts by weight of the copolymer according to the invention obtained in test No. 36.

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