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US20040219215A1 - Aqueous compositions comprising a chemical microgel associated with an aqueous polymer - Google Patents

Aqueous compositions comprising a chemical microgel associated with an aqueous polymer Download PDF

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Publication number
US20040219215A1
US20040219215A1 US10/483,202 US48320204A US2004219215A1 US 20040219215 A1 US20040219215 A1 US 20040219215A1 US 48320204 A US48320204 A US 48320204A US 2004219215 A1 US2004219215 A1 US 2004219215A1
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Prior art keywords
polymer
chemical
monomers
composition according
microgel particles
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Inventor
Bruno Bavouzet
Mathias Destarac
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Assigned to RHODIA CHIMIE reassignment RHODIA CHIMIE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DESTARAC, MATHIAS, BAVOUZET, BRUNO
Publication of US20040219215A1 publication Critical patent/US20040219215A1/en
Priority to US12/348,745 priority Critical patent/US8591949B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels

Definitions

  • the present invention relates to aqueous compositions comprising particles of chemical microgel associated with at least one bridging polymer, more particularly in the form of a viscous fluid or a gel.
  • One aim of the present invention is to propose a gel which combines the characteristics of stability not only of chemical type gels, but also of physical type gels.
  • aqueous composition comprising particles of hydrosoluble or hydrodispersible chemical microgel associated with at least one hydrosoluble or hydrodispersible bridging polymer with a chemical composition that differs from that of said particles; the quantity of chemical microgel particles being in the range 0.05% to 40% of the dry weight of the composition and the quantity of bridging polymer being such that the viscosity of the composition is at least three times, preferably at least ten times that of an aqueous solution of chemical microgel particles and that of an aqueous solution of bridging polymer under the same conditions.
  • the present invention also relates to a first process for preparing said composition, in which:
  • a chemical gel is prepared in an aqueous phase by polymerizing the desired monomer or monomers and a crosslinking agent, or by chemical post-polymerization cross-linking of a polymer;
  • the composition of the invention has the advantage of forming a gel which is at least partially or even completely reversible.
  • the rheological profile of the aqueous composition is generally shear thinning in type.
  • the viscosity reduces and increases again or may even resume the initial viscosity when shearing is stopped.
  • the rheological profile is shear thickening in nature
  • reversibility similarly results in the viscosity reducing again or even recover of the initial viscosity when shearing is stopped.
  • the composition of the invention forms a gel which preserves its rheological properties better under constraints of temperature under shear, for example, while conventional physical gels lose them.
  • the aqueous composition of the invention can be in the form of a gel. More precisely, the term “gel” means compositions with a modulus of elasticity (G′) that is greater than or equal to the loss modulus (G′′) over a frequency range in the range 1 to 10 Hz, using a cone-plate geometry; the modules were measured in the linear viscoelastic region, at 25° C., with a Rheometrics or Carrimed rheometer.
  • G′ modulus of elasticity
  • G′′ loss modulus
  • the viscosities were measured using a Carrimed type viscosimeter, with a cone-plate geometry; the measurements were made at 25° C. at a shear rate of 1 s ⁇ 1 .
  • composition pH conditions concern the composition per se prior to use, comprising the copolymer and the charged species, or associated with various other constituents necessary to obtaining complete formulations. These “conditions” can also concern the composition during its use, more specifically during use of the complete formulation.
  • polymers designates both homopolymers and copolymers.
  • the bridging polymer is termed hydrosoluble or hydrodispersible when no macroscopic phase separation phenomena are observed when it is in solution or dispersion in an aqueous phase, after one hour under the same conditions of concentration and temperature as those of the composition of the invention.
  • particles of hydrosoluble or hydrodispersible chemical microgel means particles of chemically cross-linked polymer swelled by an aqueous solution.
  • one of the first constituents of the aqueous composition of the invention is constituted by hydrosoluble or hydrodispersible particles of chemical microgel.
  • the quantity of chemical microgel particles is in the range 0.05% to 10% of the dry composition weight, preferably in the range 0.1% to 5% of the dry composition weight.
  • the number average size of the chemical microgel particles is in the range 0.3 ⁇ m to 10 mm, preferably in the range 1 ⁇ m to 1000 ⁇ m, more preferably in the range 1 ⁇ m to 100 ⁇ m.
  • the number average size is determined by optical microscopy.
  • the chemical microgel particles are constituted by at least one chemically cross-linked hydrosoluble or hydrodispersible polymer.
  • Said polymer can be obtained either directly in the cross-linked form, for example by adding at least one cross-linking agent to the monomers constituting the polymer, the cross-linking agent usually being a multifunctional monomer.
  • Said polymer can also be obtained by carrying out a chemical post-polymerization cross-linking step, i.e., cross-linking after the step for polymerizing the monomer or monomers constituting said polymer.
  • the polymer from which the chemical microgel particles are derived is such that the number of hydrosoluble motifs of said polymer represents at least 50% of the number of polymer motifs, preferably at least 80% by weight of said polymer.
  • hydrophilic motif means a monomer selected from those which, once homopolymerized with a degree of polymerization in the range 40 to 100, produces a soluble polymer under the temperature and pH conditions of the composition. More particularly, the temperature is in the range 15° C. to 35° C.
  • the polymers from which the chemical microgel particles are derived are obtained at least from non ionic, ionic or potentially ionizable (in particular under the pH conditions) hydrophilic monomers.
  • the non ionic hydrophilicity monomers are selected from: ethylene oxide; amides of linear or branched, cyclic or aromatic mono- or polycarboxylic acids, comprising at least one ethylenically unsaturated bond or derivatives thereof, such as (meth)acrylamide, N-methylol(meth)acrylamide; certain esters deriving from (meth)acrylic acid such as 2-hydroxyethyl (meth) acrylate; and vinyl esters that can produce polyvinyl alcohol blocks after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate, N-vinylpyrrolidone, used alone or as a mixture.
  • anionic or potentially anionic monomers can be cited, which carry at least one carboxylic, sulphonic, sulphuric, phosphonic, phosphoric or sulphosuccinic function, their corresponding salts, or their corresponding precursors.
  • the polymers can be obtained from at least one monomer selected from:
  • aminoacids comprising one or more ethylenically unsaturated bonds
  • vinyl sulphonic acid vinylbenzene sulphonic acid, vinylphosphonic acid, vinylidene phosphoric acid, vinylbenzoic acid, and their alkali metal salts such as sodium or potassium salts, or ammonium salts;
  • the scope of the present invention includes the use of monomers that are precursors of those just described.
  • said monomers have motifs which, once incorporated into the polymer, can be transformed, in particular by a chemical treatment such as hydrolysis, to reproduce the species cited above.
  • the ionic or potentially hydrophilic monomers are selected from cationic or potentially cationic monomers.
  • aminoalkyl (meth)acrylates aminoalkyl (meth)acrylamides
  • monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, or ethylene imine;
  • Said monomers can have a counter-ion selected from halogens, such as chlorine, sulphates, hydrosulphates, alkylsulphates, phosphates, citrates, formats, or acetates.
  • halogens such as chlorine, sulphates, hydrosulphates, alkylsulphates, phosphates, citrates, formats, or acetates.
  • cationic monomers that can form part of the composition of the cationic blocks of the copolymer that can be cited are:
  • dimethylaminoethyl(meth)acrylate dimethylaminopropyl(meth)acrylate, ditertiobutyl aminoethyl (meth)acrylate, dimethylamino methyl (meth)acrylamide, dimethylaminopropyl(meth)acrylamide;
  • trimethylammonium ethyl(meth)acrylate chloride trimethylammonium ethyl acrylate methyl sulphate, benzyldimethylammonium ethyl (meth)acrylate chloride, 4-benzoylbenzyl dimethylammonium ethyl acrylate chloride trimethylammonium ethyl (meth)acrylamido chloride, trimethylammonium vinylbenzyl chloride;
  • the scope of the present invention encompasses the use of one or more amphoteric monomers which, depending on the pH conditions, will provide a net positive, negative or zero charge. Similarly, it is possible to use one or more zwitterionic type monomers, which have a net zero charge at any pH.
  • the polymers from which the chemical microgel particles are derived can optionally be obtained from hydrophobic monomers.
  • hydrophobic monomers can be selected from:
  • esters of linear or branched, cyclic or aromatic mono- or poly-carboxylic acids comprising at least one ethylenically unsaturated bond
  • hydrophobic monomers that can be used in preparing the polymers that can be cited are:
  • esters of (meth)acrylic acid with an alcohol containing 1 to 12 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate;
  • vinyl nitriles more particularly including those containing 3 to 12 carbon atoms, in particular acrylonitrile and methacrylonitrile;
  • the polymers from which the chemical microgel particles are derived can be homopolymers or copolymers.
  • copolymers may have a random or block structure. Further, whether or not they comprise different monomers, the polymers can be linear, branched, comb-like in structure or star type in structure.
  • the chemical microgel particles are obtained by carrying out the following steps:
  • the polymers from which the chemical microgel particles are derived are advantageously obtained by using radical polymerization, although other types of polymerization are perfectly possible, such as anionic or cationic polymerization.
  • the polymers are obtained using at least one living radical polymerization step.
  • the polymerization reaction carried out to obtain them is conducted in the presence of at least one control agent especially of the xanthate, dithiocarbamate or dithioester type.
  • the polymer from which the chemical microgel particles are derived is obtained by carrying out polymerization in the aqueous phase of the desired monomers and at least one cross-linking agent. In this case, polymerization and cross-linking are carried out simultaneously.
  • the cross-linking monomers that can be used have at least two reactive functions in the selected polymerization mode.
  • at least one monomer comprising at least two ethylenically unsaturated bonds and at most 10 unsaturated bonds and known to be radically reactive is used.
  • said monomers have two ethylenically unsaturated bonds.
  • the following can in particular be cited: acrylic, methacrylic, acrylamido, methacrylamido, vinyl ester, vinyl ether, diene, styrene, alpha-methyl styrene and allyl derivatives.
  • Monomers belonging to those families are: vinyl methacrylate, methacrylic acid anhydride, allyl methacrylate, ethylene glycol dimethacrylate, phenylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene 200 dimethacylate, polyethylene glycol 400 dimethacylate, butanediol 1,3-dimethacrylate, butanediol 1.4-dimethacrylate, hexanediol 1,6-dimethacrylate, dodecanediol 1,12-dimethacrylate, glycerol 11.3-dimethacrylate, diurethane dimethacrylate, trimethylolpropane trimethacrylate.
  • Particular members of the multifunctional acrylate family that can be cited are vinyl acrylate, bisphenol A epoxy diacrylate, dipropylene glycol diacrylate, tripropyleneglycol diacrylate, polyethylene glycol 600 diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, aliphatic urethane diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, aliphatic urethane triacrylate, trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate.
  • Vinyl ethers that can be cited are vinyl crotonate, diethylene glycol divinyl ether, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether.
  • the following allyl derivatives can be cited: diallyl phthalate, diallyldimethyl ammonium chloride, diallyl malleate, sodium diallyloxyacetate, diallylphenylphosphine, diallylpyrocarbonate, diallyl succinate, N,N′-diallyltartardiamide, N,N-diallyl-2,2,2-trifluoroacetamide, the allyl ester of diallyloxyacetic acid, 1,3-diallyl urea, triallylamine, triallyl trimesate, triallyl cyanurate, triallyl trimellitate, triallyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.
  • Acrylamido derivatives that can in particular be cited are N,N′methylenebisacrylamide, N,N′-methylenebismethacrylamide, glyoxal bisacrylamide, diacrylamdoacetic acid.
  • Styrene derivatives that can be cited include divinylbenzene and 13-diisopropenylbenzene.
  • Diene monomers that can be cited are butadiene, chloroprene and isoprene.
  • Preferred cross-linking monomers are N,N′-methylenebisacrylamide, divinylbenzene and ethylene glycol diacrylate.
  • the quantity of cross-linking agent can readily be determined by the skilled person depending on the desired degree of cross-linking and such that the chemical microgel particles to be obtained finally are hydrosoluble or hydrodispersible, as defined above.
  • the polymerization reaction is carried out in the presence of at least one source of free radicals.
  • This radical polymerization initiator can be selected from initiators conventionally used in radical polymerization, such as:
  • peroxides of hydrogen such as tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butyl-peroxybenzoate, t-butylperoxyoctoate, t-butylperoxyneodecanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypival, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulphate and ammonium persulphate;
  • azo compounds such as: 2,2-azobis(isobutyronitrile), 2,2′-azobis(2-butanenitrile), 4,4′-azobis(4-pentanoic acid), 1,1′-azobis(cyclohexane-carbonitrile), 2-(t-butylazo)-2-cyanopropane, 2,2′-azobis [2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2′-azobis(2-methyl-N-hydroxyethyl]-propionamide, 2,2′-azobis(N,N′-dimethylene isobutyramidine) dichloride, 2,2′-azobis(2-amidinopropane) dichloride, 2,2′-azobis(N,N′dimethyleneisobutyramide), 2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide), 2,2′-azobis(2-methyl-N-N-[
  • redox systems comprising combinations such as mixtures of peroxides of hydrogen, and analogues with one or more iron salts, titanous salts, etc. and reducing sugars; alkali metal or ammonium persulphates, perborates or perchlorates in association with an alkali metal bisulphite and reducing sugars; alkali metal persulphate in association with an arylphosphinic acid and reducing sugars.
  • the quantity of initiator to be used is determined so that the quantity of radicals created is at most 50 mole %, preferably at most 20 mole % with respect to the quantity of polymer or control agent.
  • the temperature can be between ambient temperature and 150° C., depending on the nature of the monomers used.
  • the polymer from which the chemical microgel particles is derived is prepared by carrying out aqueous phase polymerization of the desired monomer or monomers followed by a step for cross-linking said polymer (post-polymerization cross-linking).
  • cross-linking agents cited above can be used during this step.
  • cross-linking is carried out in the presence of at least one initiator, in an amount such that the quantity of radicals created is at most 50 mole %, preferably at most 20 mole % with respect to the quantity of polymer.
  • cross-linking can consist of reacting the polymer functions together. As an example, it may concern esterification or transesterification reactions.
  • catalysts that are particular to those reactions such as acids or bases, can be added to the polymer.
  • polymer cross-linking can be carried out using multifunctional non-polymerizable compounds carrying at least one chemical function that is an antagonist to that/those carried by the polymer to be cross-linked.
  • a di-iodine compound to cross-link a polymer carrying at least one poly(2-dimethylaminoethyl acrylate) block, or glutaraldehyde to cross-link a polyvinyl type alcohol, etc.
  • the polymer is separated from the reaction mixture in conventional manner, for example by precipitation from a non-solvent.
  • the chemical microgel particles are obtained by carrying out polymerization of the desired monomers and the cross-linking agent in micro-reactors and/or with stirring and/or in the presence of at least one limiting agent, or by chemical post-polymerization cross-linking in micro-reactors and/or with stirring, of a polymer obtained by polymerization of the desired monomers or monomers.
  • said polymer from which the chemical microgel particles are derived may or may not be obtained by carrying out the polymerization in micro-reactors and/or with stirring.
  • this latter can be selected from radical transfer agents, for example compounds of the thiol type (see Sherrington, Polymer 41 (2000)) or from control agents, for example of the nitroxide type (see D H Solomon et al, Macromol. Rapid Commun. 18, 755 (1997) and Polymer 42, 5987 (2001)). Using such agents prevents macrogel formation.
  • This second implementation aims to provide access to chemical microgel particles without having to carry out a polymer grinding step.
  • polymerization is carried out in micro-reactors either with stirring or in the presence of a limiting agent, or by a combination of these possibilities.
  • micro-reactors are droplets of an emulsion, which in the present case is a reverse emulsion (water-in-oil).
  • the organic phase is composed of an organic solvent that is not miscible with water and is inert under the reaction conditions.
  • organic solvent that is not miscible with water and is inert under the reaction conditions. Examples that can be cited are hexane, heptane, isoparaffin cuts, etc.
  • the organic phase of the emulsion further comprises at least one surfactant.
  • the surfactant is selected from those that are at least partially soluble in the organic phase of the emulsion.
  • particular surfactants that can be employed in this implementation are selected from non ionic surfactants with a low HLB (more particularly 8 or less).
  • alkoxylated fatty alcohols alkoxylated triglycerides, alkoxylated fatty acids, sorbitan esters, which may have been alkoxylated, alkoxylated fatty amines; the number of alkoxylated motifs (oxyethylenated, oxypropylenated, oxybutylenated) is such that the HLB is 8 or less.
  • the polymerization reaction can also be carried out using an amphiphilic polymer to stabilize the reverse emulsion, used alone or as a mixture with one or more of said surfactants.
  • polyhydroxystearate triblock polymers polyethylene glycol-polyhydroxystearate (products from ICI's Arlacel range, for example).
  • the reverse emulsion comprises an amphiphilic polymer or a mixture of a plurality thereof.
  • the total quantity of surfactant and/or amphiphilic polymer preferably represents 2% to 10% of the oily phase weight.
  • the scope of the present invention encompasses carrying out a grinding step on the particles obtained at the end of said steps.
  • the second constituent of the composition of the invention is the bridging polymer.
  • This is a hydrosoluble or hydrodispersible polymer with a chemical nature that differs from that of the chemical microgel particles described above.
  • the bridging polymer is considered to have a different chemical composition (nature) from that of the microgel particles if the overall compositions of the polymers are different either as regards the nature of the repeating units or the respective proportions of the repeating units.
  • the bridging polymer and the chemical microgel particles are associated in an at least partially reversible manner.
  • the composition comprising the bridging polymer and the microgel particles has rheological characteristics such that the difference between the initial viscosity and the viscosity after shear treatment for 5 minutes at 100 s ⁇ 1 measured after leaving for 24 hours is 50% or less, preferably 20% or less of the initial viscosity.
  • the quantity of bridging polymer is such that the viscosity of the composition is at least three times that of an aqueous solution of chemical microgel particles and that of an aqueous solution of the bridging polymer under the same conditions (concentration, temperature).
  • the viscosity of the composition is at least ten times that of an aqueous solution of chemical microgel particles and that of an aqueous solution of bridging polymer under the same conditions.
  • the bridging polymer is constituted by at least one polymer with a mass average molar mass that is in the range 10 3 to 5 ⁇ 10 7 g/mol, more particularly in the range 10 4 to 10 7 g/mol, preferably in the range 5 ⁇ 10 5 to 5 ⁇ 10 6 g/mol.
  • Said mass average molar masses are determined using the MALLS (multi-angle light scattering) method coupled with gel permeation chromatography.
  • the bridging polymer used has a linear structure, optionally comprising pendent side chains (grafts).
  • the bridging polymer is obtained at least starting from non ionic, ionic or potentially ionizable and optionally hydrophobic monomers.
  • the bridging polymers are not cross-linked species.
  • the cross-linking agent is employed during or after producing said polymers.
  • bridging polymer is made as a function of the nature of the cross-linked polymer constituting the chemical microgel particles, in order to produce interactions between the two compounds, namely the bridging polymer and the chemical microgel particles.
  • the chemical microgel particles and the bridging polymer are to be associated by means of electrostatic type interactions, the latter are selected so that the net overall charge of the chemical microgel particles is opposite to that of the net overall charge of the bridging polymer. More precisely, when the chemical microgel particles include anionic motifs, the bridging polymer is selected so that certain of its repeating units include cationic or potentially cationic charges (for example under the pH use conditions of the composition).
  • the bridging polymer is such that it has a degree of charged monomer polymerization in the range 5 to 10.
  • At least 50 number %, preferably at least 80 number % of the monomers constituting the polymeric chain of the bridging polymer and the chemical microgel particles have no ionic charge.
  • the chemical microgel particles and the bridging polymer are associated by means of hydrophobic-hydrophobic type interactions.
  • the microgel particles and the bridging polymer comprise motifs that can associate together in the aqueous phase by means of said bonds.
  • microgel particles comprising long alkyl chains (for example C 8 to C 22 or more) with a C 6 to C 22 alkyl acrylate type bridging polymer.
  • the chemical microgel particles and the bridging polymer are associated by means of hydrogen bond type interactions.
  • the chemical microgel particles and the bridging polymer comprise motifs that can associate together in an aqueous phase via such bonds (for example, carboxylic and/or amide motifs and ether and/or alcohol and/or amine motifs).
  • the bridging polymer and the chemical microgel particles comprise carboxylic acid, alcohol, ether, or amide type functions, for example.
  • the bridging polymer comprises at least one polymer selected from biopolymers that may or may not have been chemically modified.
  • the biopolymers are selected from polysaccharides such as galactomannans, glucomannans, succinoglycans, xanthan gum, cellulose, alginates, gelatin, which may or may not have been chemically modified.
  • biopolymer non ionic, hydrophobic, anionic, cationic, . . .
  • biopolymer non ionic, hydrophobic, anionic, cationic, . . .
  • composition of the invention can be obtained by carrying out the following steps:
  • composition is obtained by carrying out the following steps:
  • the last step is carried out simply by mixing the bridging polymer and the chemical microgel particles.
  • the invention also concerns the use of the composition described above in the fields of oil or gas field working, detergents, cosmetics, and metal treatment (transformation, deformation).
  • the invention concerns formulations comprising said composition; the formulations being intended for the fields of oil or gas field working, detergents or cosmetics.
  • Step 1 Synthesis of a PAA-b-PHEA Block Copolymer (polyacrylic acid-b-polyhydroxyethyl acrylate) 5000-b-30000
  • Mn number average molar mass
  • HSA hydroxyethyl acrylate
  • AIBN azoisobutyronitrile
  • the final dry extract was 26.4% by weight.
  • Step 2 Cross-Linking of Block Copolymer
  • aqueous solution A containing 3.2% by weight of the above microgel was prepared at a pH of 7 (adjustment using an aqueous solution of molar sodium hydroxide).
  • aqueous solution B was prepared containing 0.82% of a cationic polymer, Glokill PQ (sold by RHODIA CHIMIE). Solution B was also brought to a pH of 7 using sodium hydroxide.
  • aqueous formulation C was then prepared by mixing an identical mass of A and B.
  • Step 1 Synthesis of a PAA-b-Pam Block Copolymer (polyacrylic acid-b-polyacrylamide) 5000-b-60000
  • Mn 49000.
  • Step 2 Synthesis of Microgel Based on PAA and Pam
  • the prepared product formed a clear solution in water. It could not be filtered using a 0.45 ⁇ m GPC filter, proof of the formation of a microgel.
  • aqueous solution A containing 6% by weight of the above microgel was prepared at a pH of 7 (adjustment using an aqueous solution of molar sodium hydroxide).
  • aqueous solution B was prepared containing 1.6% of a cationic polymer, Glokill PQ (sold by RHODIA CHIMIE). Solution B was also brought to a pH of 7 using sodium hydroxide.
  • aqueous formulation C was then prepared by mixing an identical mass of A and B.

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US10/483,202 2001-07-13 2002-07-15 Aqueous compositions comprising a chemical microgel associated with an aqueous polymer Abandoned US20040219215A1 (en)

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FR0109387A FR2829494B1 (fr) 2001-07-13 2001-07-13 Compositions aqueuses comprenant un microgel chimique associe a un polymere pontant, preparation et utilisation
FR01/09387 2001-07-13
PCT/FR2002/002512 WO2003006532A1 (fr) 2001-07-13 2002-07-15 Compositions aqueuses comprenant un microgel chimique associe a un polymere pontant, preparation et utilisation

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Cited By (5)

* Cited by examiner, † Cited by third party
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US20100215700A1 (en) * 2009-02-25 2010-08-26 Conopco, Inc., D/B/A Unilever Shear Gels and Compositions Comprising Shear Gels
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CN113924324A (zh) * 2019-06-05 2022-01-11 Spcm股份公司 通过凝胶法制备粉末形式的结构化聚合物的方法
WO2022169958A1 (en) * 2021-02-04 2022-08-11 Saudi Arabian Oil Company Amphiphilic branched copolymer drilling additive

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EP3078679B1 (de) * 2013-12-03 2022-08-17 LG Chem, Ltd. Supersaugfähiges polymer und herstellungsverfahren dafür
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US20100215700A1 (en) * 2009-02-25 2010-08-26 Conopco, Inc., D/B/A Unilever Shear Gels and Compositions Comprising Shear Gels
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CN113924324A (zh) * 2019-06-05 2022-01-11 Spcm股份公司 通过凝胶法制备粉末形式的结构化聚合物的方法
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EP1409571B1 (de) 2016-05-18
FR2829494B1 (fr) 2005-10-28
WO2003006532A1 (fr) 2003-01-23
NO20040108L (no) 2004-03-12
EP1409571A1 (de) 2004-04-21
NO336232B1 (no) 2015-06-22
US20090131578A1 (en) 2009-05-21
US8591949B2 (en) 2013-11-26

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