EP2294098A2 - Polymère superabsorbant retardé - Google Patents

Polymère superabsorbant retardé

Info

Publication number
EP2294098A2
EP2294098A2 EP09769078A EP09769078A EP2294098A2 EP 2294098 A2 EP2294098 A2 EP 2294098A2 EP 09769078 A EP09769078 A EP 09769078A EP 09769078 A EP09769078 A EP 09769078A EP 2294098 A2 EP2294098 A2 EP 2294098A2
Authority
EP
European Patent Office
Prior art keywords
acid
polymer
hydrolysis
mol
sap according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09769078A
Other languages
German (de)
English (en)
Inventor
Gregor Herth
Michael Schinabeck
Stefan Friedrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Construction Research and Technology GmbH
Original Assignee
Construction Research and Technology GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Construction Research and Technology GmbH filed Critical Construction Research and Technology GmbH
Publication of EP2294098A2 publication Critical patent/EP2294098A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0051—Water-absorbing polymers, hydrophilic polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0062—Cross-linked polymers

Definitions

  • the present invention relates to a superabsorbent polymer with delayed swelling and its use.
  • Superabsorbent polymers are crosslinked, high molecular weight, either anionic or cationic polyelectrolytes, which are obtainable by free-radical polymerization of suitable, ethylenically unsaturated vinyl compounds and subsequent drying measures of the resulting copolymers.
  • a hydrogel is formed with swelling and water absorption, whereby a multiple of the weight of the powdery copolymer can be absorbed.
  • Hydrogels are water-containing gels based on hydrophilic but crosslinked water-insoluble polymers, which are present as three-dimensional networks.
  • Superabsorbent polymers are thus typically crosslinked polyelectrolytes, e.g. consisting of partially neutralized polyacrylic acid. They are described in detail in the book “Modern Superabsorbent Polymer Technology” (FL Buchholz and AT Grahem, Wiley-VCH, 1998) In addition, there are a variety of patents dealing with superabsorbent polymers in more recent patent literature superabsorbent polymers have also been developed for use in building material mixtures, which have a very good action at high salt concentrations, as caused, for example, by the addition of calcium formate as an accelerator.
  • rheology jump There are some applications for dry mortar (eg as grout) or concretes (production of precast concrete), in which after their introduction into the joint or in the shape of the finished part, a sudden increase in viscosity is desired (hereinafter called rheology jump).
  • the joint mortar should be easy to bring into the joint, while he should finally be stiff and dimensionally stable in the joint.
  • a concrete for the precast industry should be easy to bring into the mold, but then as soon as possible have a solid consistency, so that can be quickly turned off.
  • the viscosity of a building material applied with water depends on the water content of the cement matrix. This is described by the water / cement value. The higher this is, the lower the viscosity of the building material.
  • the hydrogel formed from the powdery, superabsorbent copolymer by absorption of water should have as few as possible components soluble in water so as not to negatively influence the rheology properties of the building material mixtures.
  • Another problem with building material mixtures is bleeding over time; i.e. Water separates from the mixed building material mixture, accumulates on the surface and floats on top. This bleeding is generally undesirable because it also removes the need for the hydration mixing water of the building material mixture. In many applications, the evaporated water leaves an unsightly salt crust, which is generally undesirable.
  • an accelerated Abbindevorgang is also desirable.
  • a low viscosity is desired, in the joint this should then increase quickly, so that the shape is retained. The sooner this is the case, the sooner the laid tiles can be washed off without having to wash out the joint again. This would be a great relief to the user as mortar residues could be more easily removed from the joints without leaving cement streaks or attacking the surface of the tile.
  • this processing profile is set by a mixture of Portland cement (PZ) and alumina cement (TZ).
  • PZ Portland cement
  • TZ alumina cement
  • U2CO3 U2CO3
  • Another big problem with the application is the low storage stability. Namely, it occurs during storage, a shift in the rheology profile, which is understandably undesirable.
  • the early strength discussed above is economically very important.
  • the higher the early strength the faster the further layers can be applied to the floor.
  • a minimum of mixing water is necessary to achieve the necessary flowability of a leveling compound. This is difficult to combine with the desired early strength because it depends on the w / c value as described above.
  • a concentration of the pore solution after application would also be desired here.
  • a common problem in practice is the bleeding described above. This often occurs in the first hours after processing. The water at the surface evaporates and leaves an unattractive surface appearance (encrustation).
  • US 5,837,789 describes a crosslinked polymer which is used for the absorption of aqueous liquids.
  • This polymer is composed of partially neutralized monomers with monoethylenically unsaturated acid groups and optionally other monomers which are copolymerized with the first components. Described is also a process for the preparation of these polymers, wherein first the respective starting components are polymerized to a hydrogel by means of a solution or suspension polymerization. The polymer thus obtained can subsequently be crosslinked on its surface, which should preferably take place at elevated temperatures.
  • Gel particles with superabsorbent properties composed of several components are described in US Pat. No. 6,603,056 B2.
  • the gel particles comprise at least one resin which is capable of absorbing acidic aqueous solutions and at least one resin capable of absorbing basic aqueous solutions.
  • Each particle also contains at least one microdomain of the acidic resin which is in direct contact with a microdomain of the basic resin.
  • the resulting superabsorbent polymer is characterized by a defined conductivity in salt solutions, and also by a defined absorption capacity under pressure conditions.
  • the focus of EP 1 393 757 B1 is on absorbent cores for diapers of reduced thickness.
  • the absorbent cores for detecting body fluids contain particles capable of forming superabsorbent nuclei.
  • the particles are provided with surface crosslinking in order to impart individual stability to the particles, so that a defined salt flow conductivity results.
  • the said surface layer is substantially non-covalently bound to the particles and contains a partially hydrolyzable cationic polymer which is hydrolyzed in the range of 40 to 80%. This layer must be applied to the particles in an amount of less than 10 wt .-%.
  • the partially hydrolyzed polymer is a variant based on N-vinyl-alkyl-amide or N-vinyl-alkyl-imide and in particular of N-vinylformamide.
  • Superabsorbent hydrogels coated with cross-linked polyamines are also described in international patent application WO 03/0436701 A1.
  • the coating comprises cationic polymers which have been crosslinked by an addition reaction.
  • the hydrogel-forming polymer thus obtained has a residual water content of less than 10% by weight.
  • a water-absorbing polymer structure surface-treated with polycations is described in German Offenlegungsschrift DE 10 2005 018 922 A1.
  • This polymer structure which has also been contacted with at least one anion, has an absorption under a pressure of 50 g / m 2 of at least 16 g / g.
  • Superabsorbent polymers which are coated with a polyamine are the subject of WO 2006/082188 A1. Such superabsorbent polymer particles are based on a polymer with a pH> 6.
  • the hygiene articles also described in this context show a rapid uptake rate to body fluids.
  • Superabsorbent polymer particles coated with polyamines can also be found in WO 2006/082189 A1.
  • polyammonium carbonate is called.
  • the rapid absorption of body fluids by the particles in the foreground is called.
  • a typical preparation process for polymers and copolymers of water-soluble monomers, and in particular of acrylic acid and methacrylic acid, can be found in US Pat. No. 4,857,610.
  • Aqueous solutions of the respective monomers containing polymerizable double bonds are subjected to a polymerization reaction at temperatures between -10 and 120 ° C., so that a polymer layer of at least one centimeter thickness results.
  • These polymers also available have fast superabsorbent properties.
  • a delayed-release building material composition can be found in German Offenlegungsschrift DE 103 15 270 A1.
  • This composition comprises, in addition to a reactive support material, a liquid polymer compound applied thereto.
  • a carrier material hydraulic and latent hydraulic binders are mentioned, but also inorganic additives and / or organic compounds.
  • Typical polymer compounds are polyvinyl alcohols, polyvinyl acetates and polymers based on 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Due to the time-dependent detachment of Polymer component of the carrier material is a delayed release in the mixed with water mixture mixture. Associated with this is a time-controlled curing of the hydratable building material mixtures, which also allow a time-controlled "internal drying" of the building materials water-based.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • US 2006/0054056 A1 describes a process for the production of concrete products with a reduced tendency to efflorescence.
  • water-absorbing polymers find a special application. These absorbent components are added to the concrete mix in powder, liquid or granular form.
  • organic thickeners such as, for example, cellulose and derivatives thereof, but also polyvinyl alcohol and polyacrylamides and polyethylene oxides are mentioned.
  • the present invention was based on the object, in particular for building chemical applications, to develop a system and / or product which, for example. after the incorporation of the prepared building material at its intended place in the building material mixture causes a jump in the rheology or absorbs bleeding water occurring there, so that there is no phase separation and / or separation of the building material. It is also desirable to provide a system capable of absorbing any bleeding water that may be forming.
  • this is derived in particular from providing an additive to dry mortars (cement- or gypsum-based) and concretes, which makes it possible to change the w / c value in the pore solution of the setting building material mixture or of the concrete after a defined time. so that no bleeding occurs and / or a jump in the rheology in the sense of a significant increase in viscosity is achieved.
  • water stored in the respective superabsorbent polymer is not part of the pore solution, it is nevertheless available for the hydration reaction: as soon as a water deficiency occurs in the pore solution, water should be able to pass from the superabsorbent polymer into the pore solution.
  • SAP superabsorbent polymer
  • the SAP should be a polymer with anionic and / or cationic properties and a delayed swelling effect; its preparation should be carried out by polymerization of ethylenically unsaturated vinyl compounds.
  • SAP superabsorbent polymer
  • the application of the polymers according to the invention is completely surprising but not limited to building material systems. Many applications are possible which require water absorption after a defined time, especially such applications which results in a solid end product from a solution, emulsion or suspension. This idea is taken into account by the present invention by the different use variants according to the invention.
  • the term "delayed swelling effect” is to be understood as meaning that the swelling starts at the earliest after 5 minutes, ie the fluid intake begins after a time delay , preferably after more than 15 minutes, and more preferably only after more than 30 minutes, has already been known for some time in the context of hygiene articles, so that, for example, the liquid is first distributed in the diaper before it is absorbed
  • a time delay longer periods of more than 5 minutes and in particular more than 10 minutes are understood.
  • Polymerization involving a) combination of a hydrolysis-stable and a hydrolysis-labile crosslinker; and / or b) polymerizing a permanently anionic monomer and a hydrolyzable cationic monomer; and / or c) coating a superabsorbent polymer as a core with another polyelectrolyte as a shell, wherein the core polymer contains hydrolysis-stable crosslinkers; or / and d) polymerization of at least one hydrolysis-stable monomer with at least one hydrolysis-labile monomer in the presence of at least one crosslinker.
  • each of the embodiments a), b, c)) or d) may be used alone. However, it is also possible to combine the embodiments according to the invention with one another, so that a polymer according to embodiment a) can be produced in an additional process step according to embodiment c). be coated with another polyelectrolyte to adjust the time delay more precisely. This is referred to below as “mixed embodiments.” All embodiments, whether pure or mixed, have in common that the properties of the resulting time-delayed superabsorbent polymer correspond to the profile of requirements. For example, in a building material mixture, to a chemical reaction, which leads to an increase in the absorption.After the reaction, the maximum absorption is reached, which is called in the following final absorption.
  • SAPs of the invention are distinguished, in particular, by the fact that the particular monomer building blocks have been used as free acids, as salts or in a mixed form thereof.
  • the acid moieties have been neutralized after the polymerization.
  • This is advantageously carried out with the aid of sodium, potassium, calcium or magnesium hydroxide, of sodium, potassium, calcium or magnesium carbonate, ammonia, a primary, secondary or tertiary C 1-20 -alkylamine, a d-2o-alkanolamine, a Cs-s-cycloalkylamine and / or a C6-14-alkylamine, wherein the amines may have branched and / or unbranched alkyl groups having 1 to 8 carbon atoms.
  • all mixtures are also suitable.
  • the polymerization according to the present invention should have been carried out in particular as a free-radical substance, solution, gel, emulsion, dispersion or suspension polymerization.
  • Variants have proven to be particularly suitable in which the polymerization in aqueous phase has been carried out in reverse emulsion (inverse emulsion) or in inverse suspension.
  • the reaction should preferably be started with a redox initiator and / or a photoinitiator.
  • the temperature is not critical. However, it has proved to be favorable not only from an economic point of view, if the polymerization has been started at temperatures between -20 and +30 0 C. Areas between -10 and + 20 0 C and in particular between 0 and 10 ° C have been found to be particularly suitable as starting temperatures. Also with regard to the process pressure, the present invention is not limited. This is also the reason why the polymerization can ideally be carried out under atmospheric pressure and without any heat input whatsoever, which is considered advantageous by the present invention.
  • solvents are essentially not required for the polymerization reaction. However, in special cases, it can prove to be advantageous if the preparation of the superabsorbent polymers has been carried out in the presence of at least one water-immiscible solvent and in particular in the presence of an organic solvent.
  • organic solvents this should be selected from the linear aliphatic hydrocarbon series and preferably n-pentane, n-hexane and n-heptane.
  • aliphatic hydrocarbons isoparaffins
  • cycloaliphatic hydrocarbons and preferably cyclohexane and decalin or aromatic hydrocarbons, and in particular benzene, toluene and xylene, but also alcohols, ketones, carboxylic acid esters, nitro compounds, halogenated hydrocarbons, ethers, or any suitable Mixtures thereof in question.
  • Organic solvents which form azeotropic mixtures with water are particularly well suited.
  • the superabsorbent polymers of the present invention are based on ethylenically unsaturated vinyl compounds.
  • the present invention provides for selecting these compounds from the series of ethylenically unsaturated, water-soluble carboxylic acids and ethylenically unsaturated sulfonic acid monomers and their salts and derivatives and preferably acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, ⁇ -methylacrylic acid ( Crotonic acid), ⁇ -phenylacrylic acid, ⁇ -acryloxypropionic acid, sorbic acid, ⁇ -chlorosorbic acid, 2'-methylisocrotonic acid, cinnamic acid, p-chlorocinnamic acid, ⁇ -stearylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fum
  • acrylic or methacrylic sulfonic acid is at least one member of the series sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropylsulfonklare and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) in question.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • Particularly suitable nonionic monomers should be selected from the group of water-soluble acrylamide derivatives, preferably alkyl-substituted acrylamides or aminoalkyl-substituted derivatives of acrylamide or methacrylamide, and more preferably acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide, N-tertiary butylacrylamide, N-vinylformamide, N-vinylacetamide, acrylonitrile, methacrylonitrile, or any mixtures it.
  • water-soluble acrylamide derivatives preferably alkyl-substituted acrylamides or aminoalkyl-substituted
  • vinyllactams such as N-vinylpyrrolidone or N-vinylcaprolactam
  • vinyl ethers such as methylpolyethylene glycol (350 to 3000) monovinyl ethers, or those derived from hydroxybutyl vinyl ethers such as polyethylene glycol (500 to 5000) -vinyloxy-butyl ether, polyethylene glycol block-propylene glycol (500 to 5000) -vinyloxy-butyl ether, of course, in this case, mixtures come into question.
  • Variant a Combination of a hydrolysis-stable and a hydrolysis-labile crosslinker
  • the time delay is achieved by a special combination of crosslinkers.
  • the combination of two or more crosslinkers in a superabsorbent polymer per se is not new. It is discussed in detail, for example, in US Pat. No. 5,837,789.
  • the combination of crosslinkers was used to improve the antagonistic properties of absorption capacity and soluble content, as well as absorption capacity and permeability. A high absorption is promoted namely by low Vernetzermengen; but this leads to increased soluble fractions and vice versa.
  • the combination of different crosslinkers forms better products over the three properties of absorption capacity, soluble content and permeability.
  • the delay of the swelling by several minutes by a crosslinker combination and in particular to> 10 minutes was not known.
  • a time delay is set so that only the liquid is distributed in the diaper and then absorbed, it is usually in the range of a few seconds.
  • the superabsorbers of this embodiment a) according to the invention are preferably present either as anionic or cationic polyelectrolytes, but essentially not as polyampholytes.
  • Polyampholytes are polyelectrolytes which carry both cationic and anionic charges on the polymer chain. In this case, preference is therefore given to copolymers of purely anionic or purely cationic nature and not polyampholytes. However, up to 10 mol%, preferably less than 5 mol%, of the total charge of a polyelectrolyte may be replaced by opposite charges. This applies both to the case of predominantly anionic copolymers having a relatively small cationic content and conversely to predominantly cationic copolymers having a relatively small anionic content.
  • Suitable monomers for anionic superabsorbent polymers are, for example, ethylenically unsaturated, water-soluble carboxylic acids and carboxylic acid derivatives or ethylenically unsaturated sulfonic acid monomers.
  • carboxylic acid or carboxylic acid anhydride monomers are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, ⁇ -methylacrylic acid (crotonic acid), ⁇ -phenylacrylic acid, ⁇ -acryloxypropionic acid, sorbic acid, ⁇ -chlorosorbic acid, 2'-methylisocrotonic acid, cinnamic acid, p Chloromimetic acid, ⁇ -stearic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxyethylene and maleic anhydride, with acrylic acid and methacrylic acid being particularly preferred.
  • Ethylenically unsaturated sulfonic acid monomers are preferably aliphatic or aromatic vinyl sulfonic acids or acrylic or methacrylic sulfonic acids.
  • Preferred aliphatic or aromatic vinylsulfonic acids are vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid and styrenesulfonic acid.
  • acrylic or methacrylic sulfonic acids are sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, with 2-acrylamido-2-methylpropanesulfonic acid being particularly preferred.
  • All listed acids may have been polymerized as free acids or as salts.
  • a partial neutralization is possible.
  • the neutralization partially or completely be carried out only after the polymerization.
  • the neutralization of the monomers can be carried out with alkali metal hydroxides, alkaline earth metal hydroxides or ammonia.
  • any further organic or inorganic base is conceivable which forms a water-soluble salt with the acid.
  • a mixed neutralization with different bases is conceivable.
  • the neutralization with ammonia and alkali metal hydroxides and particularly preferably with sodium hydroxide is considered.
  • water soluble acrylamide derivatives are alkyl substituted acrylamides or aminoalkyl substituted derivatives of the acrylamide or the methacrylamide, e.g.
  • Acrylamide methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethylacrylamide and / or N-tertiary butylacrylamide.
  • nonionic monomers are N-vinylformamide, N-vinylacetamide, acrylonitrile and methacrylonitrile, but also vinyllactams such as N-vinylpyrrolidone or N-vinylcaprolactam and vinyl ethers such as methylpolyethylene glycol (350 to 3000) monovinyl ethers, or those derived from hydroxybutyl vinyl ether such as polyethylene glycol (500 to 5000) -vinyloxy-butyl ether, polyethylene glycol-block-propylene glycol (500 to 5000) -vinyloxy-butyl ether, and suitable mixtures thereof.
  • vinyllactams such as N-vinylpyrrolidone or N-vinylcaprolactam
  • vinyl ethers such as methylpolyethylene glycol (350 to 3000) monovinyl ethers, or those derived from hydroxybutyl vinyl ether such as polyethylene glycol (500 to 5000) -viny
  • the superabsorbent polymers according to the invention comprise at least two crosslinkers:
  • a crosslinker produces a link between two polymer chains which leads to the superabsorbent polymers forming water-swellable but water-insoluble networks.
  • One class of crosslinkers are monomers having at least two independently built-in double bonds which lead to the formation of a network.
  • a hydrolysis-stable crosslinker is to be understood according to the invention as a crosslinker which retains its crosslinking effect at all pH values when incorporated in the network.
  • the nodes of the network can not be broken by a change of the source medium.
  • the hydrolysis-labile crosslinker which can lose its crosslinking effect by changing the pH in the network.
  • An example of this is a diacrylate crosslinker which by alkaline ester hydrolysis at a high pH loses its crosslinking effect.
  • Possible hydrolysis-stable crosslinkers are N, N'-methylenebisacrylamide, N, N'-methylenebis-methacrylamide and monomers having more than one maleimide group, such as hexamethylenebismaleimide; more than one vinyl ether group-containing monomers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether and / or cyclohexanediol divinyl ether. Allylamino or allylammonium compounds having more than one allyl group, such as triallylamine and / or tetraallylammonium salts, may also be used.
  • the hydrolysis-stable crosslinkers also include the allyl ethers, such as tetraallyloxyethane and pentaerythritol triallyl ether.
  • Divinylbenzene and triallyl isocyanurate may be mentioned from the group of monomers containing more than one vinylaromatic group.
  • the hydrolysis-stable crosslinker at least one member of the series N, N'-methylenebisacrylamide, N, N'Methylenbismethacrylamid or monomers having at least one maleimide group, preferably Hexamethylenbismaleinimid, monomers having more than a vinyl ether group, preferably ethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, allylamino or allyl ammonium compounds having more than one allyl group, preferably triallylamine or a tetraallylammonium salt such as tetraallylammonium chloride, or allyl ethers having more than one allyl group such as tetraallyloxyethane and pentaerythritol triallyl ether, or monomers having vinylaromatic groups, preferably divinylbenzene and Triallyl
  • Hydrolysis-labile crosslinkers may be: poly (meth) acryl-functional monomers, such as 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, ethoxylated Bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene
  • Preferred representatives of the hydrolysis-labile crosslinkers in the preparation variant a) were compounds which were selected from the series of di-, tri- or tetra (meth) acrylates, such as 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3 - butylene glycol diacrylate, 1, 3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol-A-dimethacrylate, 1, 6- hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate , Triethylene glycol dimethacrylate,
  • crosslinkers which contain functional groups from both the class of the hydrolysis-labile and the hydrolysis-stable crosslinkers should then be counted among the hydrolysis-labile crosslinkers if they form at most one hydrolysis-stable crosslinking point.
  • Typical examples of such crosslinkers are polyethylene glycol monoallyl ether acrylate and polyethylene glycol monoallyl ether methacrylate.
  • crosslinkers having two or more double bonds there are also those which contain only one or no double bond, but there are other functional groups which can react with the monomers and which lead to crosslinking points during the production process. Two frequently used functional groups are mainly epoxy groups and amino groups.
  • crosslinkers having a double bond examples include glycidyl acrylate, allyl glycidyl ether.
  • crosslinkers having no double bond are diamines, triamines or compounds having four or more amino groups, such as ethylenediamine, diethylenetriamine, or diepoxides, such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether.
  • the polymeric product has only a low absorption capacity after short times (> 5 min, ⁇ 10 min).
  • hydrolysis-stable crosslinkers between 0.01 and 1.0 mol%, preferably between 0.03 and 0.7 mol% and particularly preferably 0.05 to 0.5 mol%, were used in process variant a). Significantly higher amounts of the hydrolysis-labile crosslinkers are required. According to the invention, from 0.1 to 10.0 mol%, preferably from 0.3 to 7 mol%, and particularly preferably from 0.5 to 5.0 mol%, were used.
  • the hydrolysis-labile network linkages formed during the polymerization are dissolved again.
  • the absorption capacity of the superabsorbent polymer according to the invention is thereby significantly increased.
  • the required quantities for the crosslinkers are to be adapted to the respective application and to be determined in application technology tests (for building material systems in particular in the time-dependent slump).
  • Cationic superabsorbent polymers contain only cationic monomers.
  • all monomers having a permanent cationic charge can be used. Permanent means again that the cationic charge remains largely stable in an alkaline medium; an ester quat, for example, is not suitable.
  • non-ionic comonomers and crosslinkers it is possible to use all monomers listed among the anionic superabsorbent polymers, the molar ratios mentioned above being used come.
  • Possible cationic monomers are: [3- (acryloylamino) -propyl] -trimethylammonium salts and / or [3- (methacryloylamino) -propyl] -trimethylammonium salts.
  • the salts mentioned are preferably in the form of halides, sulfates or methosulfates.
  • diallyldimethylammonium chloride can be used.
  • the anionic or cationic superabsorbent copolymers according to the invention can be prepared in a manner known per se by linking the monomers forming the respective structural units by free-radical polymerization. All monomers present as acid can be polymerized as free acids or in their salt form. Furthermore, the neutralization of the acids can be carried out by addition of appropriate bases also after the copolymerization; Partial neutralization before or after the polymerization is also possible. The neutralization of the monomers or the copolymers can be carried out, for example, with the bases sodium, potassium, calcium, magnesium hydroxide and / or ammonia.
  • bases are primary, secondary or tertiary and in each case branched or unbranched alkyl groups having C 1 to C 20 alkylamines, C 1 to C 20 alkanolamines, C 5 to C 8 cycloalkylamines and / or C 6 to C 14 arylamines.
  • One or more bases can be used. Preference is given to neutralization with alkali metal hydroxides and / or ammonia; Sodium hydroxide is particularly suitable.
  • the inorganic or organic bases should be selected so that they form well water-soluble salts with the respective acid.
  • the copolymerization of the monomers should preferably be carried out by free-radical bulk, solution, gel, emulsion, dispersion or suspension polymerization.
  • the products according to the invention are hydrophilic and water-swellable copolymers, aqueous-phase polymerization, reverse-emulsion polymerization (water-in-oil) and inverse suspension polymerization (water-in-oil) are preferred variants .
  • the reaction takes place as gel polymerization or as inverse suspension polymerization in organic solvents.
  • the process variant a) can also be carried out as adiabatic polymerization and started both with a redox initiator system and with a photoinitiator be. But it is also possible a combination of both variants of the initiation.
  • the redox initiator system consists of at least two components, an organic or inorganic oxidizing agent and an organic or inorganic reducing agent.
  • compounds with peroxide units are used, for example inorganic peroxides such as alkali metal and ammonium persulfate, alkali metal and ammonium perphosphates, hydrogen peroxide and its salts (sodium peroxide, barium peroxide) or organic peroxides such as benzoyl peroxide, butyl hydroperoxide or peracids such as peracetic acid.
  • inorganic peroxides such as alkali metal and ammonium persulfate, alkali metal and ammonium perphosphates, hydrogen peroxide and its salts (sodium peroxide, barium peroxide) or organic peroxides such as benzoyl peroxide, butyl hydroperoxide or peracids such as peracetic acid.
  • organic peroxides such as benzoyl peroxide, butyl hydroperoxide or peracids such as peracetic acid.
  • other oxidizing agents for example potassium permanganate, sodium and potassium chlor
  • Sulfur-containing compounds such as sulfites, thiosulfates, sulfinic acid, organic thiols (for example ethylmercaptan, 2-hydroxyethanethiol, 2-mercaptoethylammonium chloride, Thioglycolic acid) and others.
  • organic thiols for example ethylmercaptan, 2-hydroxyethanethiol, 2-mercaptoethylammonium chloride, Thioglycolic acid
  • ascorbic acid and low-valency metal salts [copper (I); Manganese (II); Iron (II)] suitable.
  • phosphorus compounds such as sodium hypophosphite can be used. Photopolymerizations are started according to their name with UV light, resulting in the decomposition of a photoinitiator.
  • benzoin and benzoin derivatives such as benzoin ethers, benzil and its derivatives such as benzil ketals, acryl diazonium salts, azo initiators such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-amidinopropane) hydrochloride and / or acetophenone derivatives are used.
  • the proportion by weight of the oxidizing and the reducing component in the case of the redox initiator systems is preferably in the range from 0.00005 to 0.5% by weight, more preferably in each case from 0.001 to 0.1% by weight.
  • this range is preferably between 0.001 and 0.1% by weight and more preferably between 0.002 and 0.05% by weight.
  • the stated weight percentages for the oxidizing and reducing component and the photoinitiators relate in each case to the mass of the monomers used for the copolymerization.
  • the selection of the polymerization conditions, in particular the amounts of initiator, always takes place with the aim of producing polymers which are as long-chain as possible. Due to the insolubility of the crosslinked copolymers, however, the determination of the molecular weights is very difficult.
  • the copolymerization is preferably carried out in aqueous solution, in particular in concentrated aqueous solution discontinuously in a polymerization vessel (batch process) or continuously after the z.
  • B. "endless belt" as described in the US-A-4857610 performed method Another option is the polymerization in a continuous or batchwise kneading reactor The process is usually conducted at a temperature between -20 and 20 0C, preferably between.. - 10 and 10 0 C started and carried out at atmospheric pressure and without external heat, wherein by the Heat of polymerization is a dependent on the monomer content maximum final temperature of 50 to 150 0 C is obtained. After the end of the copolymerization is usually a crushing of the present as a gel polymer.
  • the crushed gel is dried in the case of a laboratory scale in a convection oven at 70 to 180 0 C, preferably at 80 to 150 0 C dried. On an industrial scale, drying can also be carried out in a continuous manner in the same temperature ranges, for example on a belt dryer or in a fluidized bed dryer.
  • the copolymerization is carried out as an inverse suspension polymerization of the aqueous monomer phase in an organic solvent.
  • the procedure is preferably such that the monomer mixture dissolved in water and optionally neutralized is polymerized in the presence of an organic solvent in which the aqueous monomer phase is insoluble or sparingly soluble.
  • W / O emulsifiers water-in-oil emulsifiers
  • protective colloids based on low or high molecular weight compounds which are present in proportions of from 0.05 to 5% by weight, preferably 0, 1 to 3 wt.% (In each case based on the monomers) are used.
  • the W / O emulsifiers and protective colloids are also referred to as stabilizers.
  • stabilizers in the inverse suspension polymerization technique, such as hydroxypropylcellulose, ethylcellulose, methylcellulose, cellulose acetate butyrate blends, copolymers of ethylene and vinyl acetate, of styrene and butyl acrylate, polyoxyethylene sorbitan monooleate, laurate or stearate and block copolymers of propylene and / or or ethylene oxide.
  • organic solvents for example, linear aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, branched aliphatic hydrocarbons (isoparaffins), cycloaliphatic hydrocarbons such as cyclohexane and decalin, and aromatic hydrocarbons such as benzene, toluene and xylene are suitable.
  • linear aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, branched aliphatic hydrocarbons (isoparaffins), cycloaliphatic hydrocarbons such as cyclohexane and decalin, and aromatic hydrocarbons such as benzene, toluene and xylene are suitable.
  • alcohols, ketones, carboxylic acid esters, nitro compounds, halogen-containing hydrocarbons, ethers and many other organic solvents are also suitable. Preference is given to those organic
  • the water-swellable copolymers are initially obtained in swollen form as finely divided aqueous droplets in the organic suspension medium and are preferably isolated by removing the water by azeotropic distillation as a solid spherical particles in the organic suspension medium. After separation of the suspending agent and drying, a powdery solid remains.
  • Inverse suspension polymerization is known to have the advantage that the particle size distribution of the powders is controlled by varying the polymerization conditions can. An additional process step (grinding process) for adjusting the particle size distribution can thus be avoided in most cases.
  • the monomers and crosslinkers should be selected in accordance with the particular, sometimes specific needs of the application. For example, at high salt loads in the building material system salt-stable monomer compositions should be used, e.g. based on sulfonic acid-based monomers. The final absorption is set via the monomer composition and the hydrolysis-stable crosslinkers, while the hydrolysis-labile crosslinker influences the kinetics of the swelling. It should be noted, however, that the monomer composition and the crosslinker can also have a certain influence on the kinetics, which is different from case to case and especially less pronounced against the influence of the hydrolysis-labile crosslinker. Both the hydrolysis-stable and the hydrolysis-labile crosslinker should be incorporated uniformly according to the invention.
  • the choice of the composition of the superabsorbent polymer by the application is influenced.
  • the present invention provides sufficiently many variations and choices, and therefore it is readily possible to select suitable hydrolysis-stable or hydrolysis-labile crosslinkers, e.g. to ensure a homogeneous network.
  • Variant b) combination of a permanently anionic monomer with a hydrolyzable cationic monomer
  • the time delay of the swelling effect of the SAP is achieved by a specific combination of the monomers.
  • the superabsorbers of this embodiment b) according to the invention are present as polyampholytes.
  • Polyampholytes are polyelectrolytes which carry both cationic and anionic charges on the polymer chain.
  • the combination of cationic and anionic charge within the polymer chain forms strong intramolecular attractive forces that lead to a significant reduction in absorption capacity, or even to zero.
  • the cationic monomers were chosen to lose their cationic charge over time and become neutral or even anionic.
  • the two following reaction schemes are intended to explain this in more detail:
  • a cationic ester quat as a polymerized component of the SAP becomes an carboxylate in the course of its use by alkaline hydrolysis.
  • a cationic acrylamide derivative becomes nonionic by neutralization.
  • Suitable anionic monomers in this process variant b) are all anionic monomers already mentioned with regard to process variant a).
  • Preferred according to the invention are representatives from the series of ethylenically unsaturated water-soluble carboxylic acids and ethylenically unsaturated sulfonic acid monomers and their salts and derivatives, in particular acrylic acid, methacrylic acid, ethacrylic acid, .alpha.-chloroacrylic acid, .alpha.-cyanoacrylic acid, .beta.-methylacrylic acid (crotonic acid), .alpha.-phenylacrylic acid, .beta -Acryloxypropionklare, sorbic acid, ⁇ -chlorosorbic acid, 2'-methylisocrotonic acid, cinnamic acid, p-chlorocinnamic acid, ß-stearylic acid, itaconic acid, citraconic acid, mesacronic acid, glutaconic acid
  • Cationic monomers for case 1 in Figure 1 may be, for example, [2- (acryloyloxy) ethyl] trimethylammonium salts and [2- (methacryloyloxy) ethyl] trimethylammonium salts.
  • All polymerizable cationic esters of vinyl compounds are conceivable whose cationic charge can be eliminated by hydrolysis.
  • Cationic monomers for Case 2 in Figure 1 may be, for example, salts of 3-dimethylaminopropylacrylamide or 3-dimethylaminopropylmethacrylamide, with the hydrochloride and hydrosulfate being preferred.
  • all monomers are applicable, which are vinylic polymerizable and carry an amino function that can be protonated.
  • Preferred representatives of the cationic monomers according to the present invention are polymerizable cationic esters of vinyl compounds whose cationic charge can be cleaved by hydrolysis, preferably [2- (acryloyloxy) ethyl] trimethylammonium salts and [2- (methacryloyloxy) ethyl] methylammonium salts, or Monomers which are vinylically polymerizable and carry an amino function which can be protonated, preferably salts of 3-dimethylaminopropylacrylamide or 3-dimethylaminopropylmethacrylamide, and more preferably their hydrochloride and hydrosulfate, or mixtures thereof.
  • At least one crosslinker should be selected from the group of hydrolysis-stable crosslinkers described above.
  • the present invention also provides that the preparation of the SAP can be carried out in all variants, as already described under the embodiment a).
  • the second process variant b) according to the invention it is important to first achieve near zero absorption in demineralized water. This is achieved by selecting the right amounts of cationic and anionic monomers. Ideally, minimal uptake is achieved at a 1: 1 molar ratio of cationic to anionic monomers. For weak acids or bases, it may be necessary to set a molar distribution that differs from 1: 1 (eg, 1, 1 to 2.0: 2.0 to 1.1).
  • a low level of absorption can also be set. This is also achieved by a ratio deviating from the ratio of 1: 1 monomer composition (eg. 1, 1 to 2.0: 2.0 to 1, 1).
  • the molar ratio of anionic to cationic monomer is 0.3 to 2.0: 1, 0, preferably from 0.5 to 1, 5: 1, 0 and particularly preferably from 0.7 to 1 , 3: 1, 0.
  • crosslinkers can also influence the kinetics of the swelling.
  • the type and amount of crosslinker are also critical to the absorption behavior of the time-delayed superabsorbent polymer after complete hydrolysis / neutralization of the cationic monomers. Again, the swelling kinetics and the final absorption should and can be adapted to the respective application. Again, both the application and the raw materials of the formulation play a major role.
  • Interpenetrating network two networks are linked together. One network is formed from a polymer of cationic monomers, the second from anionic monomers. The charge should neutralize in total. It may prove convenient to additionally incorporate non-ionic monomers into the network. Interpenetrating networks are prepared by introducing a cationic (or anionic) polymer into an anionic or (cationic) monomer solution and then polymerizing. The networking should be chosen so that both polymers form a network: the submitted and the newly formed.
  • Variant c coating with an oppositely charged solution polymer
  • the time delay is achieved by a special surface treatment of the superabsorbent polymer.
  • the charged superabsorbent polymer is coated with an oppositely charged polymer.
  • a water impermeable membrane is formed which prevents swelling of the superabsorbent polymer in the first few minutes.
  • This surface treatment should over time (at least 10 to 15 minutes!) Detach from the SAP, which significantly increases the absorption capacity of the superabsorbent polymer.
  • anionic superabsorbent polymers preferably crosslinked, partially neutralized polyacrylic acids, with cationic polymers
  • cationic polymers having a molecular weight of 5 million g / mol or less are used which give a sprayable solution (viscosity) as a 10 to 20% strength aqueous solution. These are polymerized as an aqueous solution and used for surface treatment. The most common processes involve the superabsorbent polymer, e.g. in a fluidized bed, and sprayed with a polymer solution.
  • "highly cationic" polymers are used, ie those whose cationic monomers make up at least 75 mole percent of the composition.
  • the present invention favors the use of shell polymers having a molecular weight ⁇ 3 million g / mol, preferably ⁇ 2 million g / mol and more preferably ⁇ 1.5 Million g / mol, wherein the selected shell polymers should have either anionic or cationic properties. Ampholytes are not used.
  • MBIE superabsorbent polymers Another combination of cationic and anionic polyelectrolytes is MBIE superabsorbent polymers, where MBIE stands for “mixed bed ion exchange.”
  • MBIE stands for "mixed bed ion exchange.”
  • a potentially anionic superabsorbent polymer having a "Potentially anionic” means that in the embodiments of the invention the anionic superabsorbent polymer is used in acidic form. While the purely anionic superabsorbent polymers are usually about 70 percent neutralized polyacrylic acids, it uses crosslinked polyacrylic acids, which are not or only slightly neutralized.
  • the combination with a cationic polymer leads to a salt-stable product; the salts are neutralized, so to speak, by ion exchange, as shown in Figure 2 below.
  • the neutralized acid then has the corresponding osmotic pressure ( ⁇ ) for strong swelling.
  • any superabsorbent polymer can be used which has a sufficient uptake capacity, especially in cementitious systems. It can be both anionic and cationic.
  • the starting material will be called "core polymer.”
  • the polymer which is applied to the surface will be referred to hereinafter as the "shell polymer”.
  • the core polymers are anionic or cationic superabsorbent polymers, preferably in the sense of process variant a), which in particular have ⁇ 10% by weight of comonomers with opposite charge.
  • only superabsorbent polymers which are composed exclusively of hydrolysis-stable crosslinkers are used as core polymers in pure embodiment c). This variant is considered preferred. Except for the restriction in the crosslinkers corresponds to the synthesis of anionic Nuclear polymers of those described in process variant a). It can be used for the present case, all monomers already described there.
  • cationic core polymers For cationic core polymers, all monomers with a permanent cationic charge can be used. Permanent means in turn that the cationic charge is retained in an alkaline medium; an ester quat is thus unsuitable. Preference is given to [3- (acryloylamino) -propyl] -trimethylammonium salts and [3- (methacryloylamino) -propyl] -trimethylammonium salts.
  • the salts mentioned are preferably in the form of halides, methosulfates or sulfates.
  • diallyldimethylammonium chloride can be used.
  • One method is basically a classic powder coating.
  • the core polymer is charged and e.g. in a fluidized bed, set in motion.
  • the oppositely charged shell polymer is applied.
  • the product is dried.
  • This method is particularly useful when relatively small amounts of shell polymer based on the core polymer to be applied. For larger amounts, this process causes sticking of the particles and the product cakes. This leads to the fact that the surfaces are no longer homogeneously occupied. In order to apply large quantities of shell polymer, this process step must be repeated.
  • a second method is suitable: The core polymer is suspended in an organic solvent. To the suspension, the shell polymer solution is added, whereupon, for electrostatic reasons, the core polymer coats with an oppositely charged shell. This method is also advantageous for very small particles since they are difficult to handle in a fluidized bed. After the addition of the shell polymer solution, optionally the amount of water added by the solution can be distilled off azeotropically. Therefore, to be regarded as preferred organic solvents which form an azeotrope with the highest possible water content, in which the superabsorbent polymer and the shell polymer are not soluble.
  • the same solvents may be used, which are also mentioned in the process variant a) among the solvents for suspension polymerization.
  • a protective colloid as in the case of Suspension polymerization happens. It can be selected again from the protective colloids described therein.
  • a shell polymer is applied to the core polymer as described.
  • the shell polymer is preferably applied as an aqueous solution and used in particular as a sprayable solution, with solutions having a viscosity of 200 to 7500 mPas being particularly suitable.
  • Working with organic solvents is very expensive in this process, especially on an industrial scale.
  • the shell polymer Since the molecular weight of the shell polymer significantly affects the viscosity, shell polymers having a molecular weight of less than 5 million g / mol are preferred.
  • the further polyelectrolyte, ie the shell polymer has a proportion of cationic monomer> 75 mol%, preferably> 80 mol% and particularly preferably between 80 and 100 mol%.
  • the monomers are dissolved in water or dilute their commercially available aqueous solutions. Then the chain regulator (s) is / are added and the pH adjusted. Subsequently, the aqueous monomer solution is rendered inert with nitrogen and heated to the starting temperature. With the addition of the initiators, the polymerization is started and usually takes place in a few minutes.
  • the concentration of the shell polymer is chosen as high as possible, so that the amount of water to be removed is as small as possible, but the viscosity is still good to handle in the inventive method, such as spraying, coating in suspension. It may be advantageous to heat the Hüllpolymerains, since at higher temperatures, the viscosity at the same Concentration drops.
  • Suitable chain regulators are formic acid or its salts, for example sodium formate, hydrogen peroxide, compounds containing a mercapto group (R-SH) or a mercaptate group (RS-M +), where in each case the radical R is an organic aliphatic or aromatic radical having 1 to 16C May be atoms (eg, mercaptoethanol, 2-mercaptoethylamine, 2-mercaptoethylammonium chloride, thioglycolic acid, mercaptoethanesulfonate (sodium salt), cysteine, trismercaptotriazole (TMT) as the sodium salt, 3-mercaptotriazole, 2-mercapto-1-methylimidazole), compounds which are RSS -R'-group (disulfite group), where the radicals R and R 'independently of one another may be an organic aliphatic or aromatic radical having 1 to 16 carbon atoms (eg cystaminium dichloride, cysteine), phosphorus-
  • Possible shell polymers for anionic core polymers are cationic polymers which can lose their cationic charge by a chemical reaction.
  • Possible cationic monomers for this embodiment are ester quats, such as e.g. For example, [2- (acryloyloxy) ethyl] trimethylammonium salts, [2- (methacryloyloxy) ethyl] trimethylammonium salts, dimethylaminoethyl methacrylate quaternized with diethyl sulfate or dimethyl sulfate, diethylaminoethyl acrylate is quaternized with methyl chloride.
  • the chemical reaction leading to the time-delayed swelling of the SAP is an ester hydrolysis.
  • a neutralization reaction of the shell polymer is possible with the following polymers: poly-3-dimethylamino-propylacrylamide, poly-3-dimethylaminopropylmethacrylamide, polyallylamine, polyvinylamine, polyethyleneimine. All polymers are used as salts. For the neutralization of the amino function, inorganic or organic acids can be used, and their mixed salts are also suitable. All mentioned variants are included in the present invention.
  • nonionic monomers in the cationic shell polymer. All of the nonionic monomers already mentioned under process variant a) can be used.
  • This variant c) according to the invention is not limited to single-layer casings.
  • An anionic core polymer would be followed by an anionic second shell after the first cationic shell. The third shell would then be cationic again.
  • one or more cladding layers may be crosslinked.
  • at least one coating layer should have been crosslinked by means of an aqueous solution.
  • the present invention takes into account the possibility that the shell polymer in process variant c) per applied layer in an amount of 5 to 100 wt .-%, preferably from 10 to 80 wt .-% and particularly preferably in an amount of 25 to 75 % By weight, based in each case on the core polymer.
  • Another variation of the invention relates to cross-linking of the shell polymer and control of its peel rate. For this, e.g. free amino groups of the shell polymers are used.
  • the crosslinker is added after the shell polymer, preferably as an aqueous solution. In order to ensure a complete reaction of the crosslinker, it may be necessary to reheat the time-delayed superabsorbent polymer after drying, or to carry out the drying at elevated temperature.
  • crosslinkers for this form of implementation are diepoxides such as diethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether, diisocyanates (the latter having to be applied anhydrous after drying), glyoxal, glyoxylic acid, formaldehyde, formaldehyde formers and suitable mixtures.
  • diepoxides such as diethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether, diisocyanates (the latter having to be applied anhydrous after drying), glyoxal, glyoxylic acid, formaldehyde, formaldehyde formers and suitable mixtures.
  • the composition of the sheath polymer must be adapted to the core polymer. This can e.g. This is done by determining the appropriate composition. It has proven to be beneficial to set the identical molar ratios in the core and in the shell polymer; but the charges must be different. Depending on the application, however, deviations from the molar ratios may also prove positive.
  • the optimum amount of shell polymer must be determined.
  • finely structured core polymers require larger amounts of shell polymer because they have a larger surface area.
  • the molecular weight of the shell polymers may also play a role, since short-chain shell polymers dissolve better.
  • the process of surface coating c) requires more process steps than the two alternative steps a) and b).
  • the residence time in the reactor would be quite long and it is not easy to build a homogeneous layer of the shell polymer alone on the surface.
  • Variant d combination of a hydrolysis-stable and a hydrolysis-labile monomer in the presence of a crosslinker
  • the further process variant d) of the invention relates to an SAP which, after the polymerization, is composed of at least two nonionic comonomers but contains not more than 5 mol% of anionic or cationic charge.
  • these nonionic comonomers is at least one that can be converted to an ionic monomer by a chemical reaction, preferably a hydrolysis.
  • the remainder consists of permanently non-ionic monomers, which are not subject to appreciable hydrolysis even after prolonged treatment of the SAP at high pH. This then ionic monomer creates an osmotic pressure, which leads to greater swelling of the SAP.
  • An example of this is an SAP consisting of acrylamide and hydroxypropyl acrylate (HPA) and a crosslinker.
  • the polymerization is carried out as already described in the embodiment a).
  • Suitable hydrolysis-stable monomers are preferably permanently nonionic monomers, which are preferably selected from the group of water-soluble acrylamide derivatives, preferably alkyl-substituted acrylamides or aminoalkyl-substituted derivatives of acrylamide or methacrylamide, and more preferably acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N, N-N-
  • Suitable hydrolyzable monomers are selected from non-ionic monomers such as. B.
  • esters of acrylic acid or methacrylic acid such as hydroxylethyl (meth) acrylate, hydroxypropyl (meth) acrylate (as technical product isomeric mixture), esters of acrylic acid and methacrylic acid, the side chain polyethylene glycol, polypropylene glycol or copolymers of ethylene glycol and propylene glycol own, ethyl (meth) acrylate, methyl (meth) acrylate, 2-ethylhexyl acrylate.
  • amino esters of acrylic or methacrylic acid can be used, since these too are deprotonated very quickly in cementitious systems (high pH) and thus present in neutral form.
  • Possible monomers of this type are dimethylaminoethyl (meth) acrylate, tert. Butylaminoethyl methacrylate or diethylaminoethyl acrylate.
  • Suitable crosslinkers are, in particular, all hydrolysis-stable and hydrolysis-labile representatives already mentioned in connection with process variant (a), which are also used in this case in the proportions stated there.
  • the invention takes into account any combinations of the four process variants a), b), c) and d): In many cases it makes sense to combine the different variants (a + b + c + d; a + b + c; a +) b + d; b + c + d; a + c + d; a + b; a + c; a + d; b + d; c + d).
  • the step of gel polymerization or inverse suspension polymerization is particularly suitable for this purpose.
  • a further aspect of the present invention is therefore to be seen in an SAP which has been prepared by means of at least two process variants a), b), c) and d) and preferably using gel polymerization and / or inverse suspension polymerization.
  • a hydrolysis-labile crosslinker can easily be introduced in addition to the hydrolysis-stable crosslinker. If such a polymer is used as the core polymer for the surface coating, the three variants a), b) and c) are realized in the preparation of the SAP according to the invention.
  • the variants a), b) and c), or the combination of the variants a), b) and d) are preferred because they manage with only one process step (gel polymerization or inverse suspension polymerization), while embodiments, those who use the variant c) use three process steps (synthesis of the core polymer, synthesis of the shell polymer, surface coating) or lead to longer residence times in the reactor.
  • the present invention also encompasses the use of the SAP.
  • the superabsorbent polymers of the present invention are preferably used in foams, molded articles, fibers, films, cables, sealing materials, coatings, carriers for plant and fungi growth regulators, packaging materials, controlled release agent bottom additives, or in building materials, with the main focus being on present invention is for use in building materials and corresponding mixtures.
  • the present invention therefore particularly considers the use of the SAP as an additive to dry mortar mixtures, to concrete mixtures, to thick coatings with a layer thickness of 0.5 to 2 cm and in particular between 1 and 1, 5 cm, wherein all said mixtures and coatings are preferably based on cement and more preferably contain bitumen.
  • polymer dispersions used in the construction industry.
  • redispersible dispersion powders should be mentioned here.
  • the present invention therefore takes into account a specific use in which 30 min.
  • the inventive SAP maximum 70% preferably at most 60% and particularly preferably at most 50% of the maximum absorption capacity of the superabsorbent polymer.
  • This maximum absorption capacity is determined in the context of the present invention in an aqueous salt solution containing 4.0 g of sodium hydroxide or 56.0 g of sodium chloride per liter of water.
  • the main object of the present invention is a superabsorbent polymer which is characterized by special Manufacturing process and their combinations is defined and which is characterized in particular by a time-delayed swelling effect with a swelling beginning after no earlier than 5 minutes, especially in the construction chemical field of application.
  • the swelling behavior of the previously known superabsorbent polymers differs mainly in that the liquid uptake by the special structure of the SAP occurs with a time delay in the minute range. This contrasts with the hitherto known applications in the area of hygiene, where special emphasis is placed on the (body) fluids being completely absorbed by the polymer in as short a time as possible.
  • the setting and curing behavior can be controlled in particular in construction chemical masses time and also the amount of mixing water needed can be tailored to the specific application.
  • the SAP according to the invention in so-called composite units.
  • Such a composite includes the SAPs of the invention and a specific substrate.
  • the SAP and the substrate are firmly connected to each other.
  • Films made of polymers, for example of polyethylene, polypropylene or polyamide, but also metals, nonwovens, Fluffe, tissue, tissue, natural or synthetic fibers or foams are suitable substrates.
  • Such a composite contains the SAP according to the invention in an amount of about 15 to 100 wt .-%, wherein amounts between 30 and 99 wt .-% and in particular those between 50 and 98 wt .-% (each based on the total weight of the composite ) are preferred.
  • the SAP according to the invention are naturally only conditionally suitable for use in hygiene articles and in particular sanitary towels and diapers, which is why this purpose is not the actual focus of the present invention.
  • Na-AMPS 2-acrylamido-2-methylpropanesulfonic acid sodium salt
  • MbA N, N'-methylenebisacrylamide
  • MADAME-Quat [2- (methacryloyloxy) ethyl] methylammonium chloride
  • DIMAPA quat [3- (acryloylamino) -propyl] -t ⁇ methylammonium chloride
  • TEPA tetraethylenepentamine
  • HPA hydroxypropyl acrylate (mixture of isomers)
  • Polymer 1-1 Copolymer of Na-AMPS and AcA crosslinked with MbA and DEGDA
  • the solution was transferred to a plastic container having the dimensions (b ⁇ ⁇ t h) 15 cm decanted -20 cm ⁇ 10 cm, and then 16 g of a 1% 2,2'-azobis (2-amidinopropane) were added sequentially - Dihydrochloride solution, 20 g of a 1% sodium peroxodisulfate solution, 0.7 g of a 1% - Rongalit C solution, 16.2 g of a 0.1% tert-butyl hydroperoxide solution and 2.5 g of a 0.1% Fe (II) sulfate heptahydrate solution added.
  • the copolymerization was started by irradiation with UV light (two Philips tubes, Cleo Performance 40 W).
  • the hardened gel was removed from the plastic container and cut with scissors into cubes of an edge length of about 5 cm.
  • the gel cubes were minced using a conventional meat grinder, they were mixed with the Separating agent Sitren 595 (polydimethylsiloxane emulsion, Goldschmidt company) coated.
  • the release agent is a polydimethylsiloxane emulsion which has been diluted 1:20 with water.
  • the resulting gel granules of polymer 1-1 was evenly distributed on a dry grid and dried in a circulating air dryer at about 100 to 120 0 C to constant weight. There were obtained about 300 g of a white, hard granules, which was converted by means of a centrifugal mill into a powdery state.
  • the average particle diameter of the polymer powder was from 30 to 50 ⁇ m and the proportion of particles which did not pass through a sieve of mesh size 63 ⁇ m was less than 2% by weight.
  • Polymer 2-1 (with a hydrolysis-stable crosslinker): copolymer of Na-AMPS and MADAME-quat crosslinked with MbA
  • Polymer 2-2 (with a hydrolysis-stable and a hydrolysis-labile crosslinker): copolymer of Na-AMPS and MADAME-quat crosslinked with MbA and DEGDA
  • a hydrolysis-stable and a hydrolysis-labile crosslinker copolymer of Na-AMPS and MADAME-quat crosslinked with MbA and DEGDA
  • the polymerization was started by adding 15.2 g of a 20% aqueous TEPA solution and 80.0 g of a 20% aqueous sodium peroxodisulfate solution. The batch was stirred for 2 h at 70 0 C thermostat temperature, allowed to cool and bottled. At room temperature, the product had a viscosity of 2000 mPas (Brookfield, 10 rpm).
  • Polymer 3-1 Coating of an anionic superabsorbent polymer (K1a) with a cationic shell polymer H 1 k (copolymer of Na-AMPS, AcA and MbA is coated with a shell polymer of AcA and DIMAPA hydrochloride)
  • Polymer 3-2 Coating of an anionic superabsorbent polymer (K2a) with a cationic shell polymer H1 k (copolymer of Na acrylate, AcA and MbA is coated with a shell polymer of AcA and DIMAPA hydrochloride) This procedure was analogous to polymer example 3-1, except that instead of the core polymer K1 a, the same amount of core polymer K2a was submitted.
  • K2a anionic superabsorbent polymer
  • H1 k copolymer of Na acrylate, AcA and MbA is coated with a shell polymer of AcA and DIMAPA hydrochloride
  • Polymer 3-3 Coating of a cationic superabsorbent polymer (K3k) with an anionic shell polymer H2a (copolymer of DIMAPA methyl chloride quat, AcA and MbA is coated with a shell polymer of AcA and Na acrylate)
  • K3k cationic superabsorbent polymer
  • H2a anionic shell polymer of DIMAPA methyl chloride quat, AcA and MbA is coated with a shell polymer of AcA and Na acrylate
  • Example 3-1 The procedure was analogous to Example 3-1, except that instead of the core polymer K1 a, the same amount of core polymer K3k was submitted.
  • the shell polymer H2a was used as the shell polymer. Addition, azeotropic distillation and filtration were as described above.
  • Polymer 3-4 Coating of a cationic superabsorbent polymer (K3k) with an anionic shell polymer H2a with addition of a crosslinking agent for the shell polymer (copolymer of DIMAPA methyl chloride quat, AcA and MbA is coated with a shell polymer of AcA and Na acrylate and crosslinked with glyoxylic acid)
  • a crosslinking agent for the shell polymer copolymer of DIMAPA methyl chloride quat, AcA and MbA is coated with a shell polymer of AcA and Na acrylate and crosslinked with glyoxylic acid
  • the shell polymer was applied as described under 3-3.
  • the reactor temperature was reduced to 50 ° C. when the 75 ° C. azeotrope temperature was reached.
  • 50 ° C. internal temperature 2.5 g of a 50 g aqueous glyoxylic acid were added.
  • the product was filtered off and heat-treated at 120 ° C. for 2 h.
  • Polymer 3-6 Coating of an anionic core polymer based on Na acrylate / AcA (K1 a) with a three-layer shell cationic / anionic / cationic H 1 k / H2a / H1 k
  • Polymer 3-6 was made in the same way as Polymer 3-5, except that 100 g of K2a core polymer was used.
  • test solution 200 mL were placed in a 400 mL beaker and mixed with 2.00 g of the respective inventive polymer and stirred briefly with a glass rod.
  • the test was repeated with a measuring time of 24 h.
  • the determination of the time-dependent slump was carried out on a standard mortar as described in DIN EN 196-1. For this purpose, 1350 g of standard sand, 450 g of Milk CEM I 52.5 R, 0.9 g of time-delayed superabsorbent polymer according to the invention and 225 g of water were mixed according to standard. The slump was determined according to DIN EN 1015-3. Subsequently, the slump was determined over time. As a comparison, the slump was determined without the addition of time-delayed superabsorbent polymer.
  • the self-compacting concretes were mixed in the laboratory with a 50 liter compulsory mixer.
  • the efficiency of the mixer was 45%.
  • aggregates and floury substances were first homogenized in the mixer for 10 seconds before the mixing water, the flow agent and the stabilizer were then added.
  • the superabsorbent polymer according to the invention was metered in with the additives and flours.
  • the mixing time was 4 minutes.
  • the fresh concrete test slump flow rate
  • composition of the self-compacting concrete is shown in Table 2.
  • Table 2 Composition of the test mixture in kg / m 3 ; Water content 160 kg / m 3 .
  • the water content of the additives is subtracted from the total amount of mixing water.

Abstract

L'invention concerne un polymère superabsorbant (SAP) présentant des propriétés anioniques et/ou cationiques et un effet de gonflement retardé, obtenu par polymérisation de composés vinyliques éthyléniquement insaturés. Ce SAP est caractérisé en ce que son gonflement commence au plus tôt après 5 minutes, et en ce qu'il est fabriqué au moyen d'au moins une variante de procédé, sélectionnée dans la série : a) polymérisation des composants monomères en présence d'une combinaison comprenant au moins un agent réticulant stable à l'hydrolyse et au moins un agent réticulant labile à l'hydrolyse; b) polymérisation d'au moins un monomère anionique permanent et d'au moins un monomère cationique hydrolysable; c) revêtement d'un composant polymère de base avec au moins un autre polyélectrolyte en tant que polymère enveloppe; d) polymérisation d'au moins un monomère stable à l'hydrolyse avec au moins un monomère labile à l'hydrolyse, en présence d'au moins un agent réticulant. Par suite de la variabilité des trois variantes de production en ce qui concerne les matériaux de départ et les conditions du procédé, et également, du fait des possibilités de combinaison entre elles, il est possible d'obtenir, selon l'invention, des polymères superabsorbants qui conviennent en particulier pour l'utilisation dans le moussage, les corps moulés et les fibres, également comme supports pour des agents régulateurs de croissance phytosanitaires et fongicides, ainsi que pour la libération contrôlée de principes actifs, ou dans des matériaux de construction. En particulier, les polymères selon l'invention sont appropriés pour l'utilisation comme additifs de matériaux de construction.
EP09769078A 2008-06-27 2009-05-15 Polymère superabsorbant retardé Withdrawn EP2294098A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008030712A DE102008030712A1 (de) 2008-06-27 2008-06-27 Zeitverzögerte superabsorbierende Polymere
PCT/EP2009/055907 WO2009156229A2 (fr) 2008-06-27 2009-05-15 Polymère superabsorbant retardé

Publications (1)

Publication Number Publication Date
EP2294098A2 true EP2294098A2 (fr) 2011-03-16

Family

ID=41131575

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09769078A Withdrawn EP2294098A2 (fr) 2008-06-27 2009-05-15 Polymère superabsorbant retardé

Country Status (10)

Country Link
US (1) US20110095227A1 (fr)
EP (1) EP2294098A2 (fr)
JP (1) JP2011525556A (fr)
CN (1) CN102083874B (fr)
AU (1) AU2009262378B2 (fr)
BR (1) BRPI0913955A2 (fr)
CA (1) CA2725995A1 (fr)
DE (1) DE102008030712A1 (fr)
MX (1) MX2010014522A (fr)
WO (1) WO2009156229A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117735655A (zh) * 2024-02-20 2024-03-22 山东辰安化学有限公司 一种石油污水处理剂及其制备方法

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011104347A1 (fr) 2010-02-25 2011-09-01 Construction Research & Technology Gmbh Composition accélératrice de durcissement contenant des dispersants
CA2818828A1 (fr) * 2010-11-29 2012-06-07 Construction Research & Technology Gmbh Accelerateur pulverulent
CN102040987B (zh) * 2010-12-03 2013-04-24 大庆石油管理局 一种耐230℃油井水泥用缓凝剂及其制备方法
DE102011007723A1 (de) 2011-04-20 2012-10-25 Evonik Stockhausen Gmbh Verfahren zur Herstellung von wasserabsorbierenden Polymeren mit hoher Absorptionsgeschwindigkeit
FR2985732B1 (fr) * 2012-01-13 2014-01-10 Snf Sas Procede d'inertage de canalisation, de reservoir enterre ou de puits de forage mettant en oeuvre un sap
US9145340B2 (en) 2012-08-13 2015-09-29 Verdesian Life Sciences, Llc Method of reducing atmospheric ammonia in livestock and poultry containment facilities
TR201909284T4 (tr) 2012-08-13 2019-07-22 Construction Research & Technology Gmbh Bir sertleşmeyi süratlendirici bileşim için süreç.
JP6265993B2 (ja) 2012-08-13 2018-01-24 コンストラクション リサーチ アンド テクノロジー ゲーエムベーハーＣｏｎｓｔｒｕｃｔｉｏｎ Ｒｅｓｅａｒｃｈ ＆ Ｔｅｃｈｎｏｌｏｇｙ ＧｍｂＨ セメント組成物用の硬化促進剤組成物
US9961922B2 (en) 2012-10-15 2018-05-08 Verdesian Life Sciences, Llc Animal feed and/or water amendments for lowering ammonia concentrations in animal excrement
WO2014094183A1 (fr) 2012-12-21 2014-06-26 Empa Eidgenössische Materialprüfungs- Und Forschungsanstalt Béton ignifugé
CN103113508B (zh) * 2013-01-23 2015-05-20 江苏苏博特新材料股份有限公司 一种具有较慢吸液速率的高吸水树脂、其制备方法及其应用
US11254620B2 (en) 2013-08-05 2022-02-22 Verdesian Life Sciences U.S., Llc Micronutrient-enhanced polymeric seed coatings
TW201522390A (zh) 2013-08-27 2015-06-16 特級肥料產品公司 聚陰離子聚合物
WO2015035031A1 (fr) 2013-09-05 2015-03-12 Verdesian Life Sciences, Llc Compositions d'acide borique
US10519070B2 (en) 2014-05-21 2019-12-31 Verdesian Life Sciences U.S., Llc Polymer soil treatment compositions including humic acids
US10822487B2 (en) 2014-05-22 2020-11-03 Verdesian Life Sciences Llc Polymeric compositions
KR20170016386A (ko) 2014-06-02 2017-02-13 테티스, 아이엔씨. 개질된 생체중합체, 및 이의 제조 및 사용 방법
CN104177556B (zh) * 2014-08-21 2017-05-03 苏州弗克技术股份有限公司 一种稳塑剂及其制备方法
KR101578621B1 (ko) 2014-10-10 2015-12-18 연세대학교 산학협력단 우수한 금속이온 흡착능을 가지는 플레이크 형태의 고분자 흡착제 및 그 제조방법
KR101776370B1 (ko) 2014-10-10 2017-09-08 연세대학교 산학협력단 금속이온에 우수한 흡착능을 가지고 재사용이 가능한 고분자 캡슐 흡착제 및 그 제조방법
KR101776369B1 (ko) 2014-10-10 2017-09-08 연세대학교 산학협력단 금속이온에 대한 흡착능이 우수한 고분자 및 그 제조방법
CN104341545A (zh) * 2014-11-08 2015-02-11 邦丽达(福建)新材料股份有限公司 一种交联聚电解质的制备方法
CN104479066B (zh) * 2014-12-01 2017-12-05 中建商品混凝土有限公司 一种混凝土粘度调节剂及其制备方法
EP3034595B1 (fr) * 2014-12-15 2018-12-05 S.P.C.M. Sa Épaississants contenant un polymère cationique
CN107108362B (zh) 2014-12-18 2020-11-10 巴斯夫欧洲公司 用于砖瓦砂浆的建筑化学组合物
JP6682537B2 (ja) * 2014-12-22 2020-04-15 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 懸濁重合の方法
CN105037756B (zh) * 2015-08-18 2017-09-26 华南理工大学 一种具有空腔结构的高吸水树脂及其制备方法
KR102526224B1 (ko) * 2015-10-02 2023-04-26 에스디피 글로벌 가부시키가이샤 흡수성 수지 조성물 및 그 제조 방법
CN108779387B (zh) * 2015-11-23 2022-07-01 艾纳沃技术有限责任公司 涂层颗粒以及该涂层颗粒的制备方法和使用方法
US11015006B2 (en) 2016-04-14 2021-05-25 Basf Se Coated polymer particles comprising a water-swellable polymer core and a sol-gel coating
CN107759738B (zh) * 2016-08-17 2021-03-16 中国石油化工股份有限公司 一种水溶性热增黏共聚物、制备方法及应用
KR102086053B1 (ko) 2016-12-13 2020-03-06 주식회사 엘지화학 고흡수성 수지 및 이의 제조 방법
KR102086050B1 (ko) 2016-12-20 2020-03-06 주식회사 엘지화학 고흡수성 수지 및 이의 제조 방법
EP3391958B1 (fr) * 2017-04-19 2020-08-12 The Procter & Gamble Company Procédé de fabrication de particules polymères absorbant l'eau à surface enduite dans un dispositif microfluidique
WO2019112150A1 (fr) * 2017-12-08 2019-06-13 주식회사 엘지화학 Polymère absorbant et procédé de préparation associé
KR102584203B1 (ko) * 2017-12-08 2023-10-05 주식회사 엘지화학 고흡수성 수지 및 이의 제조 방법
CN109954160A (zh) * 2017-12-26 2019-07-02 安慕斯科技有限公司 一种多孔吸收锁定吸液芯体及其制备方法
WO2020037028A1 (fr) * 2018-08-16 2020-02-20 Dow Global Technologies Llc Composition de remplissage élastomère gonflable pour gazon artificiel
KR102187931B1 (ko) * 2018-11-14 2020-12-07 중앙대학교 산학협력단 급속 균열 셀프실링 특성을 가진 양이온성 고흡수율 폴리머를 포함한 자기치유 개선용 시멘트 결합재 조성물 및 양이온성 고흡수율 폴리머의 제조방법
JP2022523525A (ja) * 2019-02-27 2022-04-25 ビーエーエスエフ ソシエタス・ヨーロピア グリオキシル酸又はその縮合生成物若しくは付加生成物を含有する混合物
CN110041781A (zh) * 2019-04-07 2019-07-23 苏州百草园教育设备有限公司 一种幼儿园家具表面纳米涂层及其制备方法
US20220212995A1 (en) * 2019-04-09 2022-07-07 Nippon Shokubai Co., Ltd. Cement additive, cement admixture, cement composition, molded body, and method for improving strength of molded body
JP7248509B2 (ja) * 2019-06-10 2023-03-29 株式会社日本触媒 セメント用添加剤、セメント混和剤、セメント組成物、成形体、および成形体の強度向上方法
US11827848B2 (en) * 2019-09-20 2023-11-28 Halliburton Energy Services, Inc. Treating subterranean formations using salt tolerant superabsorbent polymer particles
CN113004550B (zh) * 2019-12-19 2022-07-12 万华化学集团股份有限公司 一种具有高通液性和低结块倾向的吸收性聚合物及其制备方法
WO2021158671A1 (fr) * 2020-02-03 2021-08-12 Northwestern University Monocristal de polyélectrolyte pour conductivité protonique
US11786884B2 (en) 2020-04-30 2023-10-17 Kimberly-Clark Worldwide, Inc. Superabsorbent polymers based on copolymers of charged monomers and neutral monomers
CN112094630B (zh) * 2020-11-17 2021-05-28 东营东方化学工业有限公司 一种复合组分树脂交联剂及其制造方法
CN113388077B (zh) * 2021-06-22 2022-05-13 西南石油大学 一种油井水泥用耐高温自交联水性环氧树脂
CN116284561A (zh) * 2021-12-21 2023-06-23 中国石油化工股份有限公司 一种缓释增粘型聚合物微球及其制备方法
CN114431339B (zh) * 2022-02-14 2023-06-27 浙江汇能生物股份有限公司 一种低添加增稳微囊化二甲酸钾饲料添加剂及其制备方法
CN114751583B (zh) * 2022-03-16 2023-04-18 黄山天马新材料科技有限公司 一种聚酯树脂生产废水处理方法
WO2024049271A1 (fr) * 2022-09-01 2024-03-07 주식회사 엘지화학 Composition polymère
CN115594858B (zh) * 2022-11-02 2023-06-16 电子科技大学长三角研究院(湖州) 可连续生长的动态软材料及其制备方法和应用
CN115779858A (zh) * 2022-12-06 2023-03-14 无锡阿科力科技股份有限公司 一种环烯烃共聚物的精制剂及其制备方法和应用
CN116445146B (zh) * 2023-04-18 2023-10-03 庆阳东祥石油科技有限公司 一种酸化解堵剂及其制备方法
CN116655943A (zh) * 2023-05-16 2023-08-29 深圳市嘉卓成科技发展有限公司 一种抗菌抗病毒水性羟基丙烯酸酯乳液的制备方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3544770A1 (de) 1985-12-18 1987-06-19 Stockhausen Chem Fab Gmbh Verfahren und vorrichtung zum kontinuierlichen herstellen von polymerisaten und copolymerisaten der acrylsaeure und/oder methacrylsaeure
US5130389A (en) * 1990-10-12 1992-07-14 Phillips Petroleum Company Superabsorbent crosslinked ampholytic ion pair copolymers containing 2-methacryloyloxyethyldimethylammonium
DE19646484C2 (de) * 1995-11-21 2000-10-19 Stockhausen Chem Fab Gmbh Flüssigkeitsabsorbierende Polymere, Verfahren zu deren Herstellung und deren Verwendung
JP3207785B2 (ja) * 1996-05-14 2001-09-10 三洋化成工業株式会社 吸水又は保水剤
US6072101A (en) 1997-11-19 2000-06-06 Amcol International Corporation Multicomponent superabsorbent gel particles
US6124391A (en) * 1998-08-18 2000-09-26 Stockhausen Gmbh & Co. Kg Superabsorbent polymers having anti-caking characteristics
AU774755B2 (en) * 1999-04-14 2004-07-08 H.B. Fuller Licensing And Financing Inc. Aqueous superarsorbent polymer and methods of use
US6514615B1 (en) * 1999-06-29 2003-02-04 Stockhausen Gmbh & Co. Kg Superabsorbent polymers having delayed water absorption characteristics
AU2002352016A1 (en) 2001-11-21 2003-06-10 Basf Aktiengesellschaft Crosslinked polyamine coating on superabsorbent hydrogels
DE60201601T2 (de) 2002-08-26 2005-11-10 The Procter & Gamble Company, Cincinnati Superabsorbierendes Polymer enthaltende absorbierende Kerne für Windeln mit verringerter Dicke und verbesserter Leistungsfähigkeit bei Flüssigkeitsaufnahme und -rückhalt
GB0224109D0 (en) 2002-10-16 2002-11-27 Cambridge Display Tech Ltd Deposition apparatus and methods
DE10314599A1 (de) * 2003-03-31 2004-10-21 Mang, Thomas, Prof. Dr. Verwendung einer vernetzten Polymerzusammensetzung als wasseraufnehmende Komponente in Dichtungs- und Absorptionsmaterialien
DE10315270A1 (de) 2003-04-03 2004-10-14 Construction Research & Technology Gmbh Pulverförmige Baustoffzusammensetzung
DE602004015098D1 (de) * 2003-05-14 2008-08-28 Schlumberger Technology Bv Selbstadaptierende zementsysteme
US20060054056A1 (en) 2004-09-13 2006-03-16 Rockwood Pigments Na, Inc. Process for producing manufactured concrete products with reduced efflorescence
TW200704689A (en) 2005-02-01 2007-02-01 Basf Ag Polyamine-coated superabsorbent polymers
TW200639200A (en) 2005-02-01 2006-11-16 Basf Ag Polyamine-coated superabsorbent polymers
DE102005018922A1 (de) * 2005-04-22 2006-10-26 Stockhausen Gmbh Mit Polykationen oberflächenbehandeltes wasserabsorbierendes Polymergebilde
US20070031499A1 (en) * 2005-07-28 2007-02-08 Huh Kang M Readily shapeable xerogels having controllably delayed swelling properties
DE102006009841A1 (de) * 2006-03-01 2007-09-06 Röhm Gmbh Additive Baustoffmischungen mit quellbaren Polymergebilden
US9120963B2 (en) * 2006-11-08 2015-09-01 Schlumberger Technology Corporation Delayed water-swelling materials and methods of use
GB2445285B (en) * 2006-12-27 2010-09-15 Schlumberger Holdings Rheology modifier for cement slurries

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009156229A3 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117735655A (zh) * 2024-02-20 2024-03-22 山东辰安化学有限公司 一种石油污水处理剂及其制备方法

Also Published As

Publication number Publication date
AU2009262378A1 (en) 2009-12-30
DE102008030712A1 (de) 2009-12-31
US20110095227A1 (en) 2011-04-28
MX2010014522A (es) 2011-07-20
AU2009262378B2 (en) 2014-01-16
CN102083874A (zh) 2011-06-01
JP2011525556A (ja) 2011-09-22
CA2725995A1 (fr) 2009-12-30
WO2009156229A2 (fr) 2009-12-30
CN102083874B (zh) 2014-08-27
BRPI0913955A2 (pt) 2015-10-20
WO2009156229A3 (fr) 2010-02-18

Similar Documents

Publication Publication Date Title
WO2009156229A2 (fr) Polymère superabsorbant retardé
EP2167443B1 (fr) Mélanges secs de matériaux de construction trempés et revenus par polymères
WO2010069607A1 (fr) Procédé de blocage de formations souterraines
EP2167444B1 (fr) Mélanges secs de matériaux de construction à base de sulfate de calcium
EP2499104B1 (fr) Mélange de mortier sec
EP2646389B1 (fr) Accélérateur pulvérulent
EP1309634B1 (fr) Copolymeres hydrosolubles ou gonflant dans l'eau, renfermant des groupes sulfo et s'epaississant par association, leur procede de production et leur utilisation
EP1984410B1 (fr) Copolymères hydrosolubles contenant des groupes sulfo, leur procédé de fabrication et leur utilisation
EP0936228B1 (fr) Copolymères soluble dans l'eau ou gonflables à l'eau, procédé de fabrication et leurs utilisation
EP2454310B1 (fr) Mélanges contenant des composés oligomères ou polymères ramifiés, leur préparation et leur utilisation
DE102004032304A1 (de) Wasserlösliche sulfogruppenhaltige Copolymere, Verfahren zu deren Herstellung und ihre Verwendung
EP1912919A1 (fr) Additif pour applications dans le domaine de la chimie du batiment
WO2008049549A2 (fr) Copolymères cationiques modifiés de façon hydrophobe
WO2011054730A2 (fr) Nanocomposites hydrosolubles à association hydrophobe (en tant qu'agents de modification de rhéologie pour applications aux produits chimiques de construction)
EP1678223A1 (fr) Copolymeres et terpolymeres solubles dans l'eau et contenant des groupes sulfo, leur production et leur utilisation comme stabilisants pour des systemes de materiau de construction aqueux et pour des systemes de peinture et de revetement a base d'eau
WO2013178560A1 (fr) Procédé de préparation d'accélérateurs solides pour des mélanges de matériaux de construction

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110127

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA RS

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150603

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20151014