CN114073940B - Core-shell particles and preparation method thereof - Google Patents

Core-shell particles and preparation method thereof Download PDF

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CN114073940B
CN114073940B CN202010842364.XA CN202010842364A CN114073940B CN 114073940 B CN114073940 B CN 114073940B CN 202010842364 A CN202010842364 A CN 202010842364A CN 114073940 B CN114073940 B CN 114073940B
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polymer
shell
shell particles
oil
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CN114073940A (en
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杨振忠
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Tsinghua University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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Abstract

The present invention relates to a core-shell particle comprising a core portion and a shell portion covering the core portion, wherein the core portion comprises a polymer and nanoparticles dispersed in the polymer, the shell portion comprising a hydrophilic polymer. The invention also relates to a preparation method of the core-shell particles and a method for separating and recycling the polymer containing carboxyl and the salt thereof in the liquid by utilizing the core-shell particles. The preparation method disclosed by the invention is simple in process, can realize batch production, and the prepared core-shell particles have strict chemical partition and can have magnetism, so that the process of separating and recovering the polymer containing carboxyl and the salt thereof in the liquid by using the core-shell particles is simple, and the recycling can be realized.

Description

Core-shell particles and preparation method thereof
Technical Field
The invention relates to a core-shell particle, a preparation method thereof and a method for separating and recycling carboxyl-containing polymer and salt thereof in liquid by using the core-shell particle.
Background
The core-shell structure combines two parts with different inner and outer parts, and the inner core and the outer shell can be two different substances, so that the composite structure has more functions. The inner core part is encapsulated inside, the whole inner core part has a supporting effect on the outer shell, and the inner core is adjustable in the type of the composition materials and the size. With the development of synthesis technology, the inner core can be solid, porous and even compounded with various molding materials, so that the inner core has more functions. The outer shell will typically cover the surface of the inner core and be composited together by covalent bonds or the like. The thickness dimension of the housing is adjustable, from nanometer to micrometer in size. The composition of the material of the shell is different, and the surface properties of the shell, such as wettability, chargeability, toughness, conductivity and the like, influence the stability and dispersibility of the whole shell, and further influence the functional application of the shell.
Various core-shell materials are widely applied to the fields of catalysis, electronics, biology, medical treatment, electronics, military industry and the like at present. In the field of environmental protection, enhanced oil recovery wastewater treatment is an important part, and a wide variety of adsorbent materials are used for enhanced oil recovery wastewater treatment. In such chemical waste solutions, a large amount of polymers such as polyacrylic acid and polyacrylamide exist, which are difficult to remove. The traditional treatment of the enhanced oil recovery wastewater mainly comprises a resin column, and the separated substances are difficult to recover and cannot be treated on a large scale. Therefore, there is great prospect in developing a granular adsorbent capable of realizing a simple adsorption and desorption process.
In the previous research, the emulsion polymerization is utilized to prepare the organic/inorganic composite particles in batches, so that the precise control of morphology can be realized, and the expansion of particle functions can be realized through modification. Depending on the composite material, the core-shell particles may be responsive. The magnetic material can realize the control of an external magnetic field, further realize magnetic response, and realize migration movement and separation recovery according to the control of the external magnetic field.
Disclosure of Invention
Problems to be solved by the invention
The existing core-shell particles still have single functions, and the preparation method of the existing core-shell particles is still complex. In addition, substances separated in the existing treatment technology of the enhanced oil recovery wastewater are difficult to recover, and large-scale treatment and recycling of resources cannot be realized.
Solution for solving the problem
Specifically, the present invention solves the technical problems of the present invention by the following means.
[1] A core-shell particle comprising a core portion and a shell portion covering the core portion, wherein the core portion comprises a polymer and nanoparticles dispersed in the polymer, the shell portion comprising a hydrophilic polymer.
[2] The core-shell particle according to item [1], wherein the nanoparticle is selected from one or more of a metal simple substance, a metal alloy, a metal oxide, an inorganic simple substance, an inorganic salt, an inorganic oxide, an inorganic carbide, an inorganic nitride, and graphene.
[3] The core-shell particle according to [1] or [2], wherein the nanoparticle has magnetism, preferably an Fe3O4 nanoparticle.
[4] The core-shell particle according to [1] or [2], wherein the polymer in the core portion is formed by polymerization of a raw material composition comprising an oil-soluble monomer including one or more selected from olefin-based, (meth) acrylamide-based and (meth) acrylate-based monomers and a crosslinking agent.
[5] The core-shell particle of item [4], wherein the oil-soluble monomer comprises one or more selected from styrene and substituted styrene.
[6] The core-shell particle according to [1] or [2], wherein the hydrophilic polymer is formed by polymerization of a raw material containing a hydrophilic monomer which is a monomer capable of undergoing radical polymerization and contains a pyridine or imidazole structure.
[7] The core-shell particle according to item [6], wherein the hydrophilic monomer comprises one or more selected from the group consisting of vinyl pyridine, alkyl vinyl pyridine, vinyl imidazole and alkyl vinyl imidazole type monomers, and the alkyl group is a linear or branched alkyl group having 1 to 10 carbon atoms.
[8] The core-shell particle according to item [7], wherein the hydrophilic monomer is one or more selected from the group consisting of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 1-vinylimidazole and 2-methyl-1-vinylimidazole.
[9] The core-shell particle of item [1], wherein the nanoparticle has magnetism, and the hydrophilic polymer comprises a pyridine or imidazole structure.
[10] A method for producing the core-shell particle of any one of [1] to [9], comprising the steps of:
mixing an oil-soluble monomer, a cross-linking agent, an oil-soluble initiator and nanoparticles to obtain an oil phase;
dissolving a surfactant in water as an aqueous phase;
mixing oil and water phases, emulsifying, and performing emulsion polymerization reaction;
after the emulsion polymerization reaction is finished, hydrophilic monomers and hydrophilic initiators are added, and the polymerization of the hydrophilic monomers is carried out to obtain core-shell particles.
[11] The method of item [10], further comprising lipophilically modifying the nanoparticle.
[12] The method according to item [10] or [11], wherein the mass ratio of the oil-soluble monomer/crosslinking agent is 5/1 to 20/1.
[13] The method according to item [10] or [11], wherein the mass ratio of the oil-soluble initiator/oil-soluble monomer is 1/500 to 1/10.
[14] The method according to item [10] or [11], wherein the hydrophilic monomer is added in an amount of 5 to 20% by mass of the oil-soluble monomer.
[15] A core-shell particle produced by the method of any one of [10] to [14 ].
[16] A method for separating and recovering a carboxyl group-containing polymer and salts thereof in a liquid, comprising the steps of:
dispersing the core-shell particles according to claim 9 with water to obtain a dispersion of core-shell particles;
mixing the obtained dispersion liquid with the liquid, and stirring the mixed liquid to realize the adsorption of the polymer in the liquid;
inserting a magnetic rod into the mixed solution, and separating and recycling core-shell particles through the magnetic rod;
and taking out the magnetic rod.
[17] The method of item [16], wherein the liquid is enhanced oil recovery wastewater.
[18] The method according to item [16] or [17], wherein the amount of the carboxyl group-containing polymer in the liquid is 0.1 to 50%; the core-shell particles are used in an amount of 0.1 to 50% by weight relative to the weight of the liquid.
[19] The method according to item [16] or [17], wherein the speed of stirring is in the range of 15-60 rpm/min; the stirring time is in the range of 30-120 min.
[20] The method according to item [16] or [17], wherein the magnetic strength of the magnetic rod is in the range of 0.5 to 1.5T.
[21] The method according to item [16] or [17], wherein the magnetic rod is inserted into the mixed solution and then allowed to stand for a period of time of 1 to 30 minutes.
[22] The method according to item [16] or [17], wherein the magnetic rod is taken out and then inserted into hot water, held for a while, and then taken out, scraped off the particles, and the particles are dried and reused; the temperature of the hot water is in the range of 50-90 ℃; the holding time is in the range of 10-30 min.
[23] The method according to item [16] or [17], wherein the carboxyl group-containing polymer and its salt comprise one or more of polyacrylic acid and its block copolymer and hydrolyzed polyacrylamide-based polymer.
[24] The use of the core-shell particle according to item [9] for separating and recovering a polymer having a carboxyl group and a salt thereof in a liquid.
[25] The use according to item [24], wherein the liquid is enhanced oil recovery wastewater.
ADVANTAGEOUS EFFECTS OF INVENTION
The core-shell particles have strict chemical partition and magnetism, can realize magnetic response and can be controlled by an external magnetic field. The preparation method can prepare core-shell particles in batches through one-step emulsion polymerization, and has simple synthesis process. The core-shell particles of the invention are used for separating and recovering the polymer containing carboxyl and the salt thereof in the liquid, thus realizing the recycling of resources.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
< terms and definitions >
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optionally" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
< core Shell particle >
It is an object of the present invention to provide a core-shell particle comprising a core portion and a shell portion covering the core portion, wherein the core portion comprises a polymer and nanoparticles dispersed in the polymer, the shell portion comprising a hydrophilic polymer.
a. Core portion
The core portion of the core-shell particles of the present invention comprises a polymer and nanoparticles dispersed in the polymer, and there is no particular limitation on the polymer and nanoparticles, and a person skilled in the art can select an appropriate polymer and nanoparticle as needed.
In one embodiment, the polymer is formed from a polymerization of a feedstock composition comprising an oil-soluble monomer and a crosslinking agent. Preferably, the oil-soluble monomer includes one or more selected from olefin-based, (meth) acrylamide-based, (meth) acrylate-based monomers. Non-limiting examples of the olefinic monomers are vinyl acetate, acrylonitrile, styrene, p-methylstyrene, alpha-methylstyrene, p-methoxystyrene, 4-chloromethylstyrene, 4-t-butylstyrene, divinylbenzene, and 4-vinylbiphenyl; non-limiting examples of the (meth) acrylamide-based monomer are N-phenyl acrylamide, N-phenyl methacrylamide, N-benzyl acrylamide, N- (4-chlorophenyl) acrylamide, N-t-butyl acrylamide, N-dodecyl acrylamide, N-octadecyl acrylamide, N-diethyl acrylamide and N, N-dibutyl acrylamide; non-limiting examples of the acrylic monomers are vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl acrylate, t-butyl methacrylate, n-butyl methacrylate, 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, oligoethylene glycol methyl ether methacrylate and polyethylene glycol methyl ether acrylate.
In a preferred embodiment, the oil-soluble monomer comprises one or more selected from styrene and substituted styrene. The substituent in the substituted styrene is selected from one or more of halogen, alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, aryl and heteroaryl; the alkyl and alkoxy groups are preferably straight or branched groups having 1 to 20, preferably 1 to 10 carbon atoms, and may be further substituted by halogen; the alkenyl, alkenyloxy and alkynyl groups are preferably straight-chain or branched groups having from 2 to 20, preferably from 2 to 10, carbon atoms and may be further substituted by halogen; the aryl and heteroaryl groups are preferably aromatic groups having 6 to 20, preferably 6 to 10 carbon atoms, and may be further substituted with halogen; the heteroatom in the heteroaryl group may be selected from O, N, S. The substituted styrene is preferably benzyl chlorostyrene.
In a preferred embodiment, the oil-soluble monomers are styrene and benzyl chlorostyrene.
In a preferred embodiment, the crosslinking agent comprises one or more selected from divinylbenzene, trimethylolpropane triacrylate, diethyl 1, 4-benzenediacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, glycerol dimethacrylate or ethylene glycol dimethacrylate.
The inorganic nano particles are selected from one or more of metal simple substances, metal alloys, metal oxides, inorganic simple substances, inorganic salts, inorganic oxides, inorganic carbides, inorganic nitrides and graphene. Preferably, the metal simple substance is selected from any of Pt, au, ag, cu, fe, co, ni, al, ca, ba, ce, the metal alloy is selected from Ag-Cu and Au-Cu, and the metal oxide is selected from TiO 2 、ZnO、Fe 2 O 3 、Fe 3 O 4 、Al 2 O 3 、BaTiO 3 、BaSnO 3 、MnFe 2 O 4 The inorganic simple substance is selected from C, si, and the inorganic simple substance isThe salt is selected from CdS, cdSe, cdTe, agCl, caCO 3 、BaSO 4 The inorganic oxide is SiO 2 The inorganic carbide is SiC, and the inorganic nitride is Si 3 N 4 、C 3 N 4 。
In a preferred embodiment, the nanoparticle is magnetic, more preferably Fe 3 O 4 And (3) nanoparticles.
The nanoparticles are present in an amount of 5 to 50% by weight, preferably 10 to 30% by weight, based on the weight of the polymer in the core portion.
b. Shell part
The shell portion of the core-shell particles of the present invention contains a hydrophilic polymer, and the hydrophilic polymer is not particularly limited, and a suitable hydrophilic polymer may be selected as required by those skilled in the art.
In one embodiment, the hydrophilic polymer of the shell portion may be attached to the polymer of the core portion by chemical bonds.
In one embodiment, the hydrophilic polymer is formed from polymerization of a feedstock comprising hydrophilic monomers. Preferably, the hydrophilic monomer includes a monomer capable of undergoing radical polymerization and containing a pyridine or imidazole structure. More preferably, the hydrophilic monomer comprises one or more selected from the group consisting of vinyl pyridine, alkyl vinyl pyridine, vinyl imidazole and alkyl vinyl imidazole, the alkyl group being a straight or branched chain alkyl group having 1 to 10 carbon atoms, preferably having 1 to 5 carbon atoms. More preferably, the hydrophilic monomer is one or more selected from the group consisting of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 1-vinylimidazole and 2-methyl-1-vinylimidazole.
In a preferred embodiment, the core-shell particles according to the invention, in which the nanoparticles have magnetic properties, the hydrophilic polymer comprises a pyridine or imidazole structure, are useful for separating and recovering carboxyl-containing polymers and salts thereof in liquids, particularly polymers in enhanced oil recovery wastewater, and the core-shell particles can be recycled.
More preferably, the nanoparticle in the core-shell particle according to the present invention has magnetic properties, the hydrophilic polymer is selected from the group consisting of polyvinylpyridine and polyvinylimidazole, and the polymer contained in the core portion is a crosslinked copolymer of styrene and benzyl chlorostyrene.
The core-shell particles according to the invention are spherical, for example true or near true, with a well-defined core-shell zonal structure, with a particle size in the range from 0.1 to 500 μm and preferably from 1 to 100 μm. The thickness dimension ratio between the core and the shell is in the range of 1 to 100, and preferably 50 to 80.
< preparation method of core Shell particle >
One of the purposes of the present invention is to provide a method for preparing core-shell particles by a one-step emulsion polymerization method and subsequent modification.
According to the preparation method of the core-shell particles, an oil phase formed by mixing oil-soluble monomers, a cross-linking agent, an initiator and oil-dispersible particles and a water phase containing a surfactant form stable emulsion through emulsification. Stable organic/inorganic composite particles are formed by the emulsion polymerization process, which is the core portion. If hydrophilic monomers are added at the beginning of polymerization, a layer of hydrophilic polymer is formed at the oil-water interface, which is a shell portion, because residual free radicals still exist on the surface of the polymer at the interface. And after the polymerization is finished, repeatedly washing with deionized water and ethanol to obtain the core-shell particles.
In one embodiment, the method comprises the steps of:
mixing an oil-soluble monomer, a cross-linking agent, an oil-soluble initiator and nanoparticles to obtain an oil phase;
dissolving a surfactant in water as an aqueous phase;
mixing oil and water phases, emulsifying, and performing emulsion polymerization reaction;
after the emulsion polymerization reaction is finished, hydrophilic monomers and hydrophilic initiators are added, and the polymerization of the hydrophilic monomers is carried out to obtain core-shell particles.
The preparation method according to the invention also optionally comprises lipophilic modification of the nanoparticles. The oleophilic modification can be performed by grafting a monomer on the surface of the inorganic nano-particles, and the grafted monomer can be selected from olefin monomers, silane coupling agents with oleophilic chain segments and compounds capable of reacting with rubber. Preferably, non-limiting examples of the olefinic monomers include divinylbenzene, styrene, long chain olefins; the silane coupling agent with the lipophilic chain segment is a silane coupling agent with an alkyl chain, a benzene ring or a double bond; non-limiting examples of the compound capable of reacting with rubber include bis- [ (triethoxysilyl) -propyl ] tetrasulfide, bis- [ (triethoxysilyl) -propyl ] disulfide, thiocyanopropyltriethoxysilane, gamma-mercaptopropyl trimethoxysilane, 3- (Xin Xianliu group) propyltriethoxysilane, 3-hexanoylthio-1-propyltriethoxysilane, and gamma-aminopropyl triethoxysilane.
According to the preparation method of the present invention, the oil-soluble monomer is a monomer as given in the description of the polymer contained in the core portion above.
In one embodiment, the oil-soluble initiator is one or more selected from azo-type initiators and peroxide initiators. Non-limiting examples of the azo-based initiator are azobisisobutyronitrile and azobisisoheptonitrile; non-limiting examples of such peroxide initiators are dibenzoyl peroxide, lauroyl peroxide, N-dimethylaniline, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate and t-butyl peroxyvalerate.
In a preferred embodiment, the mass ratio of the oil-soluble monomer/crosslinker is from 5/1 to 20/1, preferably from 8/1 to 15/1, more preferably 10/1.
In a preferred embodiment, the oil-soluble initiator/oil-soluble monomer mass ratio is 1/500 to 1/10, preferably 1/100 to 1/20, more preferably 1/100.
In a preferred embodiment, the surfactant comprises one or more selected from cationic surfactants, anionic surfactants and nonionic surfactants. Non-limiting examples of the cationic surfactant are octadecyl amine hydrochloride, dioctadecyl amine hydrochloride, N-dimethyloctadecyl amine hydrochloride, and dodecyltrimethyl ammonium bromide; non-limiting examples of the anionic surfactant are sodium dodecyl sulfate, sodium dodecyl sulfonate, and sodium dodecyl benzene sulfonate; non-limiting examples of the nonionic surfactant are span 80, tween 80, octylphenol polyoxyethylene ether, and dodecanol polyoxyethylene ether.
In a preferred embodiment, the mass ratio of the water to the oil phase is from 1/1 to 20/1, preferably from 5/1 to 10/1, more preferably 5/1.
In a preferred embodiment, the surfactant is used in an amount of 0.1 to 2%, preferably 0.1 to 1%, by mass of water.
In a preferred embodiment, the emulsification is carried out under mechanical stirring at a speed of 8000-15000rpm/min, preferably 12000rpm/min; the emulsifying time is 20-180s, preferably 60s.
In a preferred embodiment, the temperature of the emulsion polymerization is 60-90 ℃, preferably 70 ℃; the time of the emulsion polymerization is 1 to 8 hours, preferably 4 hours.
According to the preparation method of the present invention, the hydrophilic monomer is as given in the description of the shell part above.
In a preferred embodiment, the hydrophilic monomer is added in an amount of 5 to 20% by mass, preferably 10% by mass, of the oil-soluble monomer.
In a preferred embodiment, the time of polymerization of the hydrophilic monomer is 1 to 4 hours, preferably 2 hours.
In a preferred embodiment, the hydrophilic initiator is one or more selected from persulfates and azo-type initiators. The persulfate initiator is selected from potassium persulfate, ammonium persulfate and sodium persulfate; the azo initiator is selected from azo diisobutyl amidine hydrochloride, azo diisopropyl imidazoline and azo dicyanovaleric acid.
In a preferred embodiment, the polymerization of the hydrophilic monomer is carried out under conditions that maintain the temperature unchanged.
The production method according to the present invention further optionally includes a step of separating core-shell particles from the dispersion obtained after polymerization of the hydrophilic monomer; the dispersion obtained after polymerization of the hydrophilic monomer is preferably centrifuged, washed with ethanol and water, and dried to obtain core-shell particles. The preferred drying method is spray drying or freeze drying.
In a preferred embodiment, the nanoparticle is magnetic and the hydrophilic monomer comprises a pyridine or imidazole structure-containing monomer. In this embodiment, the preparation method of the present invention mixes magnetic particles and monomers together, obtains an organic/inorganic polymer composite sphere having magnetic response through emulsion polymerization and serves as a core, and grafts functional polymer through a modification process on the outside. Therefore, the core-shell particles can realize the adsorption separation of specific substances, and simultaneously have magnetic response which can be controlled by an external magnetic field, so as to achieve the aim of separating and recovering polymers containing carboxyl and salts thereof in liquid, in particular to the polymers in the enhanced oil recovery wastewater.
< method for separating and recovering carboxyl group-containing Polymer and salt thereof in liquid >
With the wide application of polymer flooding as a relatively mature technology in various large oil fields, the treatment of enhanced oil recovery wastewater becomes a problem to be solved urgently. The polymer used in polymer flooding at present is mainly partially hydrolyzed polyacrylamide, the molecular weight of the polymer is in the range of 100-500 ten thousand, and the content of the polymer in the enhanced oil recovery wastewater is in the range of 200-800 mg/L. The presence of polymers in the wastewater increases the viscosity of the liquid, so that the stability of colloidal particles therein is improved, and thus a longer time is required for natural settling, and in addition, the presence of anionic polymers interferes with the use effect of conventional flocculants, thus enhancing the key of oil recovery wastewater treatment in which the polymers are separated and recovered.
One of the purposes of the invention is to provide a method for separating and recovering polymers and salts thereof containing carboxyl groups in liquid, especially polymers in enhanced oil recovery wastewater, wherein the method utilizes core-shell particles in the preferred embodiment of the invention to adsorb and separate the polymers and salts thereof containing the carboxyl groups, and realizes the adsorption and desorption processes at different temperatures through the hydrogen bond action of pyridine or imidazole structures and carboxyl groups or carboxylate ions on the polymer particles. The magnetic rod is used for controlling the process, so that the external field regulation and control of the core-shell particle as the adsorption material can be realized, and the purposes of adsorbing and separating the polymer containing carboxyl and the salt thereof in the liquid, particularly the polymer in the enhanced oil recovery wastewater and recycling the core-shell particle are realized.
In one embodiment, the method comprises the steps of:
dispersing the core-shell particles according to the invention with water to obtain a dispersion of core-shell particles;
mixing the obtained dispersion liquid with the liquid, and stirring the mixed liquid to realize the adsorption of the polymer in the liquid;
inserting a magnetic rod into the mixed solution, and separating and recycling core-shell particles through the magnetic rod;
and taking out the magnetic rod.
In one embodiment, the above steps are optionally repeated to achieve the best separation recovery result. For example, after the magnetic rod is taken out, the dispersion of core-shell particles is optionally added again to the liquid and mixed, and then the magnetic rod is inserted again and taken out, and this is repeated a plurality of times.
In one embodiment, the liquid is enhanced oil recovery wastewater. The amount of the carboxyl group-containing polymer and its salt in the liquid is 0.001% to 50% by mass of the liquid, and the preferable range is 0.01% to 40%.
In one embodiment, mixing of the core-shell particles and adsorption of the polymer in the liquid is achieved by pouring the dispersion of the particles into a reservoir containing the liquid; preferably, the volume of the liquid storage tank is 1-11m 3 Within a range of (2).
In one embodiment, the core-shell particles are used in a dispersion of the core-shell particles in an amount of 0.01 to 0.5kg/L (w/v), preferably 0.1 to 0.2kg/L (w/v), relative to water.
In one embodiment, the core-shell particles are used in an amount of 0.1 to 50% by weight relative to the weight of the liquid.
In a preferred embodiment, the speed of agitation is in the range of 15-60 rpm/min; the stirring time is in the range of 30-120 min.
In a preferred embodiment, the carboxyl group-containing polymer and salts thereof include, but are not limited to, one or more of carboxyl group-containing polyacrylic acid and block copolymers thereof, and hydrolyzed polyacrylamide-based polymers.
In a preferred embodiment, the magnetic strength of the magnetic rod is in the range of 0.5-1.5T.
In a preferred embodiment, the magnetic rod is inserted into the mixture and then allowed to stand for a period of time ranging from 1 to 60 minutes, preferably from 5 to 30 minutes; more preferably 10-20min.
In a preferred embodiment, the magnetic rod is taken out and then placed in hot water for a period of time, then the magnetic rod is taken out, the core-shell particles are separated from the magnetic rod, and the particles are dried and reused; the temperature of the hot water is in the range of 50-90 ℃; the holding time of the magnetic rod in hot water is in the range of 10-30 min.
In a preferred embodiment, the method of drying the particles is oven drying or freeze drying.
In the embodiment that the liquid is the enhanced oil recovery wastewater, the method for separating and recovering the polymer containing the carboxyl and the salt thereof by using the core-shell particles can adsorb and separate the polyacrylic acid and the polyacrylamide polymer in the enhanced oil recovery wastewater, can treat the enhanced oil recovery wastewater in batches, and realizes the recycling of the core-shell particles.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the invention will become apparent to those skilled in the art upon reading the description herein, and such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
Example 1
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 0.6g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g of Divinylbenzene (DVB) and 0.12g of azobisisobutyronitrile are mixed to form an oil phase. 0.1g of sodium dodecyl sulfate was dissolved as a surfactant in 43g of water as an aqueous phase. The water-oil phase was shear emulsified for 1min under mechanical stirring at 12000rpm, nitrogen was introduced and the temperature was raised to 70℃for polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝10％。
250mg of 1-vinylpyridine was dissolved in 10mL of water, and 2.5mg of potassium persulfate was added at the same time, and when the polymerization was carried out for 4 hours, the above-mentioned solution was added, and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles A.
2) Separating and recovering polymer in the waste water of oil recovery
1kg of the above-mentioned core-shell particles A were dispersed in 10L of water to obtain a dispersion, 10L of enhanced oil recovery wastewater was injected into a liquid storage tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 30min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 50 ℃, standing for 10min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Example 2
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 1.2g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g of Divinylbenzene (DVB) and 0.12g of azobisisobutyronitrile are mixed to form an oil phase. 0.11g of sodium dodecyl sulfate was dissolved as a surfactant in 47g of water as an aqueous phase. Mechanically stirring the water phase and the oil phaseThe mixture was stirred at 12000rpm, emulsified for 1min under shear, nitrogen was introduced, and the temperature was raised to 70℃to carry out polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝20％。
250mg of 1-vinylpyridine was dissolved in 10mL of water, while 2.5mg of potassium persulfate was added. When the polymerization was carried out for 4 hours, the above solution was added and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles B.
2) Separating and recovering polymer in the waste water of oil recovery
2kg of the above-mentioned core-shell particles B were dispersed in 10L of water to obtain a dispersion, 10L of enhanced oil recovery wastewater was injected into a liquid storage tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 30min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 50 ℃, standing for 10min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Example 3
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 1.8g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g of Divinylbenzene (DVB) and 0.12g of azobisisobutyronitrile are mixed to form an oil phase. 0.12g of sodium dodecyl sulfate was dissolved as a surfactant in 51g of water as an aqueous phase. The water-oil phase was shear emulsified for 1min under mechanical stirring at 12000rpm, nitrogen was introduced and the temperature was raised to 70℃for polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝30％。
250mg of 1-vinylimidazole was dissolved in 10mL of water, while 2.5mg of potassium persulfate was added. When the polymerization was carried out for 4 hours, the above solution was added and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles C.
2) Separating and recovering polymer in the waste water of oil recovery
1kg of the above-mentioned core-shell particles C were dispersed in 10L of water to obtain a dispersion, 10L of enhanced oil recovery wastewater was injected into a liquid storage tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 60min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 50 ℃, standing for 10min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Example 4
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 0.6g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g of Divinylbenzene (DVB), 0.12g of azobisisobutyronitrile and the mixture to form an oil phase. 0.1g of sodium dodecyl sulfate was dissolved as a surfactant in 43g of water as an aqueous phase. The water-oil phase was shear emulsified for 1min under mechanical stirring at 12000rpm, nitrogen was introduced and the temperature was raised to 70℃for polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝10％。
250mg of 1-vinylimidazole was dissolved in 10mL of water, while 2.5mg of potassium persulfate was added. When the polymerization was carried out for 4 hours, the above solution was added and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles D.
2) Separating and recovering polymer in the waste water of oil recovery
1kg of the above-mentioned particles D were dispersed in 10L of water to obtain a dispersion, 10L of enhanced oil recovery wastewater was injected into a liquid storage tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 120min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 50 ℃, standing for 10min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Example 5
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 0.6g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g of Divinylbenzene (DVB) and 0.12g of azobisisobutyronitrile are mixed to form an oil phase. 0.1g of sodium dodecyl sulfate was dissolved as a surfactant in 43g of water as an aqueous phase. The water-oil phase was shear emulsified for 1min under mechanical stirring at 12000rpm, nitrogen was introduced and the temperature was raised to 70℃for polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝10％。
250mg of 2-vinylimidazole was dissolved in 10mL of water, while 2.5mg of potassium persulfate was added. When the polymerization was carried out for 4 hours, the above solution was added and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles E.
2) Separating and recovering polymer in the waste water of oil recovery
1kg of the above-mentioned core-shell particles E were dispersed in 10L of water to obtain a dispersion, 10L of enhanced oil recovery wastewater was injected into a liquid storage tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 30min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 50 ℃, standing for 10min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Example 6
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 0.6g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g Divinylbenzene (DVB), 0.12g azobisisobutyronitrile blend groupForming an oil phase. 0.1g of sodium dodecyl sulfate was dissolved as a surfactant in 43g of water as an aqueous phase. The water-oil phase was shear emulsified for 1min under mechanical stirring at 12000rpm, nitrogen was introduced and the temperature was raised to 70℃for polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝10％。
250mg of 2-vinylimidazole was dissolved in 10mL of water, while 2.5mg of potassium persulfate was added. When the polymerization was carried out for 4 hours, the above solution was added and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles F.
2) Separating and recovering polymer in the waste water of oil recovery
1kg of the above-mentioned core-shell particles F were dispersed in 10L of water to obtain a dispersion, 10L of enhanced oil recovery wastewater was injected into a liquid storage tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 30min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 90 ℃, standing for 10min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Example 7
1) Preparation of core-shell particles
2.75g of styrene (St), 2.75g of benzyl chlorostyrene (VBC), 0.6g of ferroferric oxide nanoparticles (Fe 3 O 4 ) 0.5g of Divinylbenzene (DVB) and 0.12g of azobisisobutyronitrile are mixed to form an oil phase. 0.1g of sodium dodecyl sulfate was dissolved as a surfactant in 43g of water as an aqueous phase. The water-oil phase was shear emulsified for 1min under mechanical stirring at 12000rpm, nitrogen was introduced and the temperature was raised to 70℃for polymerization. Wherein m (Fe) 3 O 4 )/m(St+VBC+DVB)＝10％。
250mg of 1-vinylimidazole was dissolved in 10mL of water, while 2.5mg of potassium persulfate was added. When the polymerization was carried out for 4 hours, the above solution was added and the polymerization was continued for 12 hours. Washing with ethanol, and vacuum drying or freeze drying to obtain core-shell particles G.
2) Separating and recovering polymer in the waste water of oil recovery
1kg of the above-mentioned core-shell particles G were dispersed in 10L of water to obtain a dispersion, 10L of wastewater was injected into a liquid tank, and then the dispersion was also injected therein. Stirring at 20rpm/min for 30min to make the core-shell particles adsorb the polymer particles. Then stopping stirring, inserting a magnetic rod, and standing for 10min to enable the core-shell particles adsorbed with the polymer particles to be adsorbed on the magnetic rod. Transferring the magnetic rod into hot water with the temperature of 90 ℃, standing for 30min, and then lifting the magnetic rod. Scraping off the core-shell particles adsorbed on the magnetic rod, repeatedly washing the core-shell particles with ethanol and water, drying, and recycling.
Examples 1-7 show that the core-shell particles prepared by the preparation method of the core-shell particles can be precisely controlled in structure, can be prepared in batch and large-scale, are simple in reaction, can treat the enhanced oil recovery wastewater in batch, and realize the adsorption separation of polyacrylic acid and polyacrylamide polymers. After the enhanced tertiary oil recovery wastewater is treated, the polymer value is reduced to below 0.1 percent.
Industrial applicability
The core-shell particles of the present invention have a wide range of industrial applications, such as wastewater treatment, and in particular for the separation and recovery of polymers in enhanced oil recovery wastewater. The preparation method of the invention can be used for preparing core-shell particles in large scale industrially.

Claims (21)

1. A core-shell particle for separating and recovering a carboxyl group-containing polymer and salts thereof in a liquid, comprising a core portion and a shell portion covering the core portion, wherein the core portion comprises a polymer and nanoparticles dispersed in the polymer, the shell portion comprises a hydrophilic polymer; wherein the nanoparticle has magnetic properties and the hydrophilic polymer comprises a pyridine or imidazole structure;
wherein the polymer in the core portion is polymerized from a feedstock composition comprising an oil-soluble monomer comprising one or more selected from the group consisting of olefin, (meth) acrylamide, and (meth) acrylate monomers, and a crosslinker; the hydrophilic polymer is formed by polymerizing a raw material containing a hydrophilic monomer, wherein the hydrophilic monomer is a monomer capable of undergoing free radical polymerization and containing pyridine or imidazole structure, the hydrophilic monomer comprises one or more selected from vinyl pyridine, alkyl vinyl pyridine, vinyl imidazole and alkyl vinyl imidazole monomers, and the alkyl is a straight-chain or branched-chain alkyl with 1-10 carbon atoms.
2. The core-shell particle of claim 1 wherein the nanoparticle is selected from one or more of a simple metal, a metal alloy, a metal oxide.
3. The core-shell particle of claim 1 or 2 wherein the nanoparticle is Fe 3 O 4 And (3) nanoparticles.
4. The core-shell particle of claim 1 wherein the oil-soluble monomer comprises one or more selected from styrene and substituted styrene.
5. The core-shell particle of claim 1 wherein the hydrophilic monomer is one or more selected from the group consisting of 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 1-vinylimidazole, and 2-methyl-1-vinylimidazole.
6. A method of preparing the core-shell particle of any one of claims 1-5, comprising the steps of:
mixing an oil-soluble monomer, a cross-linking agent, an oil-soluble initiator and nanoparticles to obtain an oil phase;
dissolving a surfactant in water as an aqueous phase;
mixing oil and water phases, emulsifying, and performing emulsion polymerization reaction;
after the emulsion polymerization reaction is finished, hydrophilic monomers and hydrophilic initiators are added, and the polymerization of the hydrophilic monomers is carried out to obtain core-shell particles.
7. The method of claim 6, further comprising lipophilically modifying the nanoparticle.
8. The method according to claim 6 or 7, wherein the mass ratio of the oil-soluble monomer/crosslinking agent is 5/1 to 20/1.
9. The method of claim 6 or 7, wherein the mass ratio of oil-soluble initiator/oil-soluble monomer is 1/500-1/10.
10. The method according to claim 6 or 7, wherein the hydrophilic monomer is added in an amount of 5 to 20% by mass of the oil-soluble monomer.
11. A core-shell particle prepared by the method of any one of claims 6-10.
12. A method for separating and recovering a carboxyl group-containing polymer and salts thereof in a liquid, comprising the steps of:
dispersing the core-shell particles according to claim 1 with water to obtain a dispersion of core-shell particles;
mixing the obtained dispersion liquid with the liquid, and stirring the mixed liquid to realize the adsorption of the polymer in the liquid;
inserting a magnetic rod into the mixed solution, and separating and recycling core-shell particles through the magnetic rod;
and taking out the magnetic rod.
13. The method of claim 12, wherein the liquid is enhanced oil recovery wastewater.
14. The method according to claim 12 or 13, wherein the amount of the carboxyl group-containing polymer and its salt in the liquid is 0.1-50% of the liquid mass; the core-shell particles are used in an amount of 0.1 to 50% by weight relative to the weight of the liquid.
15. The method of claim 12 or 13, wherein the speed of agitation is in the range of 15-60 rpm/min; the stirring time is in the range of 30-120 min.
16. The method of claim 12 or 13, wherein the magnetic strength of the magnetic rod is in the range of 0.5-1.5T.
17. The method according to claim 12 or 13, wherein the magnetic rod is inserted into the mixed solution and then allowed to stand for a period of time, the standing time being 1 to 30 minutes.
18. A method according to claim 12 or 13, wherein the magnetic rod is taken out and placed in hot water for a period of time, then the magnetic rod is taken out, the core-shell particles are separated from the magnetic rod, and the particles are dried and reused; the temperature of the hot water is in the range of 50-90 ℃; the holding time is in the range of 10-30 min.
19. The method of claim 12 or 13, wherein the carboxyl-containing polymer and salts thereof comprise one or more of polyacrylic acid and block copolymers thereof and hydrolyzed polyacrylamide polymers.
20. Use of the core-shell particles according to claim 1 for the separation and recovery of polymers containing carboxyl groups and salts thereof in liquids.
21. The use of claim 20, wherein the liquid is enhanced oil recovery wastewater.
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