+

WO2009040359A1 - Mélanges de matériaux de construction à prise hydraulique contenant des substances lipophiles microencapsulées - Google Patents

Mélanges de matériaux de construction à prise hydraulique contenant des substances lipophiles microencapsulées Download PDF

Info

Publication number
WO2009040359A1
WO2009040359A1 PCT/EP2008/062716 EP2008062716W WO2009040359A1 WO 2009040359 A1 WO2009040359 A1 WO 2009040359A1 EP 2008062716 W EP2008062716 W EP 2008062716W WO 2009040359 A1 WO2009040359 A1 WO 2009040359A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomers
weight
total weight
use according
microcapsules
Prior art date
Application number
PCT/EP2008/062716
Other languages
German (de)
English (en)
Inventor
Bogdan Moraru
Marc Rudolf Jung
Stefan Becker
Timo Mangel
Joachim Pakusch
Robert Rupaner
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Priority to EP08804629A priority Critical patent/EP2203397A1/fr
Publication of WO2009040359A1 publication Critical patent/WO2009040359A1/fr

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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0004—Microcomposites or nanocomposites, e.g. composite particles obtained by polymerising monomers onto inorganic materials
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0055—Water-insoluble 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/29—Frost-thaw resistance

Definitions

  • the present invention relates to a novel use of microcapsules comprising a capsule wall of polymer and a lipophilic substance as a capsule core, which has its melting point ⁇ 120 0 C and their boiling point> 100 0 C, as freeze-thaw stability additives in hydraulically setting building material mixtures.
  • hollow microspheres are water-filled hollow particles with a polystyrene shell. They are obtained by allowing core / shell polymers to swell with a polymethacrylic acid core and a polystyrene shell in aqueous base. It is essential that the trapped in the hollow particles water diffuses out of the capsules, so that in principle cavities are enclosed in the concrete. It is thus a defined entry of pores.
  • microcapsules with a wall material based on polymethyl methacrylate and waxes as core material in mineral moldings is known from EP 1029018 and DE-A-10 2004 005912.
  • the waxes used hereafter serve as latent heat storage material, since they absorb heat from the environment by the melting process and release it only on solidification. If the microcapsules are used in amounts above 10% by weight, based on the mineral binder, they bring about a perceptible regulation of the room temperature. They are used in particular in non-structural applications such as gypsum plaster, since the high microcapsule content has an influence on the mechanical properties.
  • the present invention was based on new freeze-thaw stability additives for hydraulically setting building material mixture as an object. Another object was to provide a light incorporation of freeze-thaw stabilizers into concrete that was virtually independent of external conditions, while the mechanical properties of the concrete should not be adversely affected.
  • microcapsules comprising a capsule wall of polymer and a lipophilic substance as a capsule core, which has its melting point ⁇ 120 0 C and their boiling point> 100 0 C, found as frost-thaw stability additives in hydraulically setting building material mixtures.
  • the capsule core is thus solid or liquid depending on the temperature.
  • the present invention is not based on the principle of the defined gas input, but rather it was found that lipophilic
  • the microcapsules used according to the invention comprise a capsule core and a capsule wall made of polymer.
  • the capsule core consists predominantly, to more than 95% by weight, of lipophilic substance. Depending on the preparation process and the selected protective colloid, this may also be part of the microcapsules. Thus, up to 15% by weight, preferably from 1 to 10% by weight, based on the total weight of the microcapsules, may be protective colloid.
  • the microcapsules on the surface of the polymer have the protective colloid.
  • the average particle size of the capsules (Z agent determined by means of light scattering) is 0.5 to 50 ⁇ m, preferably 0.5 to 30 ⁇ m, in particular 0.5 to 10 ⁇ m.
  • the weight ratio of capsule core to capsule wall is generally from 50:50 to 95: 5. Preferred is a core / wall ratio of 70:30 to 93: 7.
  • Lipophilic substances are compounds which have a solubility of less than 30 g / liter in water at 25 ° C. and normal pressure.
  • the lipophilic substances which are suitable according to the invention have a boiling point> 100 ° C. and a melting point ⁇ 120 ° C., preferably ⁇ 100 ° C., in particular ⁇ 80 ° C.
  • Suitable lipophilic substances for the use according to the invention are, for example:
  • aliphatic hydrocarbon compounds such as saturated or unsaturated C2o-Cioo hydrocarbons which are branched or preferably linear, e.g. such as n-eicosane, n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane, n-nonacosane, n-tricontane, n-tetracontane, n Pentacontane, n-hexacontane, n-heptacontan, n-octacontan, n-nonacontan, n-hectan and cyclic hydrocarbons, eg Cyclooctane, cyclodecane;
  • aromatic hydrocarbon compounds such as naphthalene, biphenyl, o- or m-terphenyl, Ci-C4o-alkyl-substituted aromatic hydrocarbons
  • saturated or unsaturated C 12 -C 30 -fatty acids such as lauric, palmitic, stearic or behenic acid, preferably eutectic mixtures of decanoic acid with e.g. Myristic, palmitic or lauric acid;
  • Fatty alcohols such as stearyl alcohol, myristyl alcohol, mixtures such as coconut fatty alcohol and the so-called oxo alcohols, which are obtained by hydroformylation of ⁇ -
  • C6-C3o-fatty amines such as tetradecylamine, hexadecylamine or eicosylamine;
  • Esters such as C 1 -C 10 -alkyl esters of fatty acids, such as stearyl stearate, and preferably their eutectic mixtures;
  • waxes such as montan acid waxes, montan ester waxes, carnauba wax, polyethylene wax, oxidized waxes, polyvinyl ether wax, ethylene vinyl acetate wax or Fischer-Tropsch wax waxes.
  • n-alkanes having a purity of greater than 80% or of alkane mixtures, as obtained as a technical distillate and commercially available as such is advantageous.
  • the capsule wall is preferably made of a thermosetting polymer.
  • thermosetting wall materials are to be understood that do not soften due to the degree of crosslinking, but decompose at high temperatures.
  • Suitable thermosetting wall materials are, for example, crosslinked formaldehyde resins, crosslinked polyureas, crosslinked polyurethanes and crosslinked methacrylic and acrylic ester polymers. Also suitable are uncrosslinked methacrylic and acrylic ester polymers.
  • Formaldehyde resins are understood as meaning reaction products of formaldehyde with
  • Triazines such as melamine carbamides such as urea
  • Phenols such as phenol, m-cresol and resorcinol
  • Amino and amido compounds such as aniline, p-toluenesulfonamide, ethyleneurea and guanidine,
  • formaldehyde resins are urea-formaldehyde resins, urea-resorcinol-formaldehyde resins, urea-melamine resins and melamine-formaldehyde resins.
  • C 1 -C 4 -alkyl, in particular methyl ethers of these formaldehyde resins and the mixtures with these formaldehyde resins are preferred.
  • melamine-formaldehyde resins and / or their methyl ethers are preferred.
  • the resins are used as prepolymers.
  • the prepolymer is still soluble in the aqueous phase and migrates in the course of the polycondensation at the interface and surrounds the oil droplets.
  • Processes for microencapsulation with formaldehyde resins are well known and described for example in EP-A-562 344 and EP-A-974 394.
  • Capsule walls of polyureas and polyurethanes are also of the
  • Copier paper known here.
  • the capsule walls are created by implementation of Nhb groups or OH-carrying reactants with di- and / or polyisocyanates.
  • Suitable isocyanates are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-methylenebis (phenyl isocyanate) and 2,4- and 2,6-toluene diisocyanate.
  • polyisocyanates such as biuret derivatives, polyuretonimines and isocyanurates.
  • Suitable reactants are: hydrazine, guanidine and its salts, hydroxylamine, di- and polyamines and amino alcohols.
  • Such interfacial polyaddition processes are known, for example, from US Pat. Nos. 4,021,595, EP-A 0 392 876 and EP-A 0 535 384.
  • the capsule wall is preferably a polymer containing at least 30 wt .-%, preferably at least 40 wt .-%, and up to 100 wt .-%, preferably at most 90 wt .-%, in particular at most 85 wt .-% and completely more preferably at most 80 wt .-% of at least one monomer selected from the group comprising Ci-C24-alkyl esters of acrylic and methacrylic acid, acrylic acid, methacrylic acid and maleic acid (monomers I), copolymerized, based on the total weight of the monomers.
  • the polymers of the capsule wall preferably contain at least 10% by weight, preferably at least 15% by weight, preferably at least 20% by weight and generally at most 70% by weight, preferably at most 60% by weight and in particular more preferably Form at most 50 wt .-% of one or more bi- or polyfunctional monomers which are insoluble or sparingly soluble in water (monomers II), copolymerized, based on the total weight of the monomers.
  • the polymers may contain up to 40% by weight, preferably up to 30% by weight, in particular up to 20% by weight, of other monomers III in copolymerized form.
  • the capsule wall is composed only of monomers of groups I and II.
  • Suitable monomers I are C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid (monomers Ia). Furthermore, the unsaturated C3 and C4 carboxylic acids such as acrylic acid, methacrylic acid and maleic acid (monomers Ib) are suitable. Particularly preferred monomers I are methyl, ethyl, n-propyl and n-butyl acrylate and / or the corresponding methacrylates. Iso-propyl, isobutyl, sec-butyl and tert-butyl acrylate and the corresponding methacrylates are preferred. Generally, the methacrylates and methacrylic acid are preferred.
  • the microcapsule walls are composed of 25% by weight to 75% by weight of maleic acid and / or acrylic acid, in particular methacrylic acid.
  • Suitable monomers II are bi- or polyfunctional monomers which are insoluble or sparingly soluble in water but have good to limited solubility in the lipophilic substance. Low solubility is to be understood as meaning a solubility of less than 60 g / l at 20 ° C.
  • Bi- or polyfunctional monomers are understood to mean compounds which have at least two non-conjugated ethylenic double bonds.
  • divinyl and polyvinyl monomers come into consideration. They cause a crosslinking of the capsule wall during the polymerization.
  • One or more divinyl monomers and one or more polyvinyl monomers can be polymerized in.
  • monomer II used is a mixture of divinyl and polyvinyl monomers, the proportion of polyvinyl monomers being from 2 to 90% by weight, based on the sum of divinyl and polyvinyl monomers.
  • the proportion of polyvinyl monomers is preferably from 5 to 80% by weight, preferably from 10 to 60% by weight, based on the sum of divinyl and polyvinyl monomers.
  • Suitable divinyl monomers are divinylbenzene and divinylcyclohexane.
  • Preferred divinyl monomers are the diesters of diols with acrylic acid or methacrylic acid, furthermore the diallyl and divinyl ethers of these diols. Examples which may be mentioned are ethanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, methallyl methacrylamide, allyl acrylate and allyl methacrylate. Particularly preferred are propanediol, butanediol, pentanediol and hexanediol diacrylate and the corresponding methacrylates.
  • Preferred polyvinyl monomers are the polyesters of polyols with acrylic acid and / or methacrylic acid, furthermore the polyallyl and polyvinyl ethers of these polyols or trivinylcyclohexane and trivinylbenzene. Preference is given to trimethylolpropane triacrylate and methacrylate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, pentaerythritol triacrylate and pentaerythritol tetraacrylate and their technical mixtures.
  • divinyl and polyvinyl monomers such as butanediol diacrylate and pentaerythritol tetraacrylate, hexanediol diacrylate and pentaerythritol tetraacrylate, butanediol diacrylate and trimethylolpropane triacrylate, as well as hexanediol diacrylate and trimethylolpropane triacrylate.
  • Suitable monomers III are other monomers which are different from the monomers I and II, such as vinyl acetate, vinyl propionate, vinylpyridine and styrene or ⁇ -methylstyrene.
  • monomers such as itaconic acid, vinylphosphonic acid, maleic anhydride, 2-hydroxyethyl acrylate and methacrylate, acrylamido-2-methylpropanesulfonic acid, methacrylonitrile, acrylonitrile, methacrylamide, N-vinylpyrrolidone, N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
  • the capsule wall is constructed from
  • Alkyl esters of acrylic and methacrylic acid, acrylic acid, methacrylic acid and maleic acid
  • the capsule wall is constructed from
  • Monomers Ib ⁇ 25% by weight, based on the total weight of all monomers I, II and III,
  • the capsule wall is constructed from
  • the microcapsules suitable according to the invention can be prepared by a so-called in situ polymerization.
  • the microcapsules and their preparation are known from EP-A-457 154, DE-A-10 139 171, DE-A-102 30 581 and EP-A-1 321 182, to which reference is expressly made.
  • the microcapsules are prepared by preparing a stable oil-in-water emulsion from the monomers, a radical initiator, a protective colloid and the lipophilic substance to be encapsulated. Stable in this case means that there is no doubling of the average droplet size within one hour.
  • the free-radical polymerization of the monomers is initiated by heating and controlled by further increase in temperature, wherein the resulting polymers form the capsule wall, which encloses the lipophilic substance.
  • the polymerization is conducted at 40 to 150 ° C, by preferably at 60 to 120 ° C.
  • the dispersion and polymerization temperature should be above the melting temperature of the lipophilic substances.
  • the polymerization is expediently continued for a time of up to 2 hours in order to lower residual monomer contents.
  • This can be achieved physically in a manner known per se by distillative removal (in particular via steam distillation) or by stripping with an inert gas.
  • distillative removal in particular via steam distillation
  • stripping with an inert gas can be done chemically, as described in WO 9924525, advantageously by redox-initiated polymerization, as described in DE-A-4 435 423, DE-A-4419518 and DE-A-4435422.
  • microcapsules having an average particle size in the range from 0.5 to 100 .mu.m it being possible to adjust the particle size in a manner known per se by means of the shearing force, the stirring rate, the protective colloid and its concentration.
  • Preference for incorporation into hydraulically setting building material mixture microcapsules having an average particle size in the range of 0.5 to 50 .mu.m, preferably 0.5 to 30 .mu.m, in particular 0.5 to 10 microns (Z means by light scattering).
  • the microcapsules are prepared in the presence of at least one organic or inorganic protective colloid.
  • organic and inorganic protective colloids may be ionic or neutral.
  • Protective colloids can be used both individually and in mixtures of several identically or differently charged protective colloids.
  • Organic protective colloids are preferably water-soluble polymers, since they reduce the surface tension of the water from 73 mN / m to a maximum of 45 to 70 mN / m and thus ensure the formation of closed capsule walls and microcapsules with preferred particle sizes in the range of 0.5 to 50 microns, preferably 0.5 to 30 microns, in particular 0.5 to 10 microns, form.
  • Organic neutral protective colloids are, for example, cellulose derivatives such as hydroxyethylcellulose, methylhydroxyethylcellulose, methylcellulose and carboxymethylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, gum arabic, xanthan, sodium alginate, casein, polyethylene glycols, polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and also methylhydroxypropylcellulose.
  • Preferred organic neutral protective colloids are polyvinyl alcohol and partially hydrolyzed polyvinyl acetates and methylhydroxypropyl cellulose.
  • organic anionic protective colloids are polymethacrylic acid, ligninsulfonates, the copolymers of sulfoethyl acrylate and methacrylate, sulfopropyl acrylate and methacrylate, N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acid and vinylsulfonic acid and maleic acid.
  • Preferred organic anionic protective colloids are polymethacrylic acid, ligninsulfonates, the copolymers of sulfoethyl acrylate and methacrylate, sulfopropyl acrylate and methacrylate, N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acid and vinylsulfonic acid and maleic acid.
  • Preferred organic anionic protective colloids are
  • a Pickering system can consist of the solid particles alone or in addition of auxiliaries which improve the dispersibility of the particles in water or the wettability of the particles by the lipophilic phase.
  • the inorganic solid particles may be metal salts, such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese.
  • metal salts such as salts, oxides and hydroxides of calcium, magnesium, iron, zinc, nickel, titanium, aluminum, silicon, barium and manganese.
  • These include magnesium hydroxide, magnesium carbonate, magnesium oxide, calcium oxalate, calcium carbonate, barium carbonate, barium sulfate, titanium dioxide, aluminum oxide, aluminum hydroxide and zinc sulfide.
  • Silicates, bentonite, hydroxyapatite and hydrotalcites are also mentioned.
  • Particularly preferred are highly disperse silicas, magnesium pyrophosphate and tricalcium phosphate.
  • the Pickering systems can both be added to the water phase first, as well as added to the stirred oil-in-water emulsion. Some fine, solid particles are produced by precipitation as described in EP-A-1 029 01
  • the highly dispersed silicas can be dispersed as fine, solid particles in water. But it is also possible to use so-called colloidal dispersions of silica in water. Such colloidal dispersions are alkaline, aqueous mixtures of silica. In the alkaline pH range, the particles are swollen and stable in water. For use of these dispersions as Pickering system, it is advantageous if the pH of the oil-in-water emulsion is adjusted to pH 2 to 7 with an acid.
  • the protective colloids are used in amounts of from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the water phase.
  • Organic protective colloids are preferably used in amounts of from 0.1 to 10% by weight, based on the water phase of the emulsion.
  • organic neutral protective colloids are preferred. Particular preference is given to OH-bearing protective colloids such as polyvinyl alcohols and partially hydrolyzed polyvinyl acetates.
  • the dispersing conditions for preparing the stable oil-in-water emulsion are preferably chosen in a manner known per se such that the oil droplets have the size of the desired microcapsules.
  • microcapsule dispersions obtained by means of polymerization give, as described in WO 2006/092439, a free-flowing capsule powder when spray-dried.
  • the spray desiccant and spray aids described therein are expressly incorporated by reference.
  • Microcapsules which are suitable according to the invention are described in more detail in EP-A 1 421 243, DE 101 63 162, WO 2005/116559 and WO 2006/092439, in particular in the context of the examples.
  • the latent heat storage materials used in this case also show a solid / liquid phase transition in the required temperature range.
  • a high purity of the substances is additionally advantageous, since this leads to particularly good transformation enthalpies.
  • As part of The present invention has shown that a high purity is not required, but especially an increased stability of the microcapsule in the mixing and curing process is advantageous, which is probably given by the solidified capsule core material.
  • microcapsules can be incorporated as a powder, as a paste and as a microcapsule dispersion in the hydraulically setting building material mixture. In this case, it is advantageous to use the microcapsule dispersion obtained directly during production in order to save additional insulating steps.
  • the building material mixture gives a mineral molding.
  • This is understood to mean that the shaped body of a mixture of cement, water, additives and, if appropriate, auxiliaries after shaping, is formed by hardening the cement-water mixture as a function of time, optionally under the effect of elevated temperature.
  • the aggregates are usually made of granular or fibrous, natural or artificial rock (gravel, sand, glass or mineral fibers), in special cases also of metals or organic aggregates or mixtures of said aggregates, with particle sizes or fiber lengths that suit the intended use are adapted in a conventional manner. Frequently, for the purpose of coloring and colored pigments are also used as surcharges.
  • Suitable auxiliaries are, in particular, those substances which accelerate or retard the hardening or which influence the elasticity or porosity of the solidified mineral shaped body. These are in particular polymers, as z. From US-A 4 340 510, GB-PS 15 05 558, US-A 3 196 122, US-A 3 043 790, US-A 3 239 479, DE-A 43 17 035 DE-A 43 17 036, JP-A 91/131 533 and other documents are known.
  • the present invention further relates to hydraulically setting building material mixtures containing 0.1 to 5 wt .-% microcapsules based on cement, wherein the microcapsules comprises a capsule wall of polymer and a lipophilic substance as a capsule core, the melting point ⁇ 120 0 C and their boiling point> 100 0 C.
  • the microcapsules comprises a capsule wall of polymer and a lipophilic substance as a capsule core, the melting point ⁇ 120 0 C and their boiling point> 100 0 C.
  • a 40% strength by weight microcapsule dispersion based on conventional concrete blocks, this means that from 0.1 to 3.5% by volume of the microcapsule dispersion is used to produce a m 3 concrete block.
  • Example 1 Water phase: 1298 g of water 662 g of a 5% strength by weight solution of methyl hydroxyethyl cellulose 165 g of a 10% strength by weight aqueous polyvinyl alcohol solution (degree of hydrolysis:
  • the above water phase was presented. After addition of the oil phase was dispersed with a high-speed dissolver at 3500 rpm. After 40 minutes of dispersion, a stable emulsion of particle size 2 to 12 microns in diameter was obtained. The emulsion was heated with stirring with an anchor raker in 60 minutes at 70 0 C, within a further 60 minutes at 85 0 C and held at 85 0 C for one hour. Feed 1 was added to the resulting microcapsule dispersion with stirring. Feed 2 was metered in with stirring over 90 minutes while being cooled to room temperature. Then it was neutralized with sodium hydroxide solution. The resulting microcapsule dispersion had a solids content of 42% and an average particle size of 4.5 microns (measured with Fraunhoferbeugung, volume average).
  • alkali-stabilized silica sol (specific surface area approx.
  • the water phase was initially introduced at 70 ° C., into which the molten and homogeneously mixed oil phase was added and dispersed for 40 minutes with a high-speed dissolver stirrer (disk diameter 5 cm) at 3500 rpm.
  • Addition 1 was added.
  • the emulsion was heated with stirring with an anchor raker in 60 minutes at 70 0 C, within a further 60 minutes at 85 0 C and held at 85 0 C for one hour.
  • Feed 1 was added to the resulting microcapsule dispersion with stirring.
  • Feed 2 was metered in with stirring over 90 minutes while being cooled to room temperature. Then it was neutralized with sodium hydroxide solution.
  • a microcapsule dispersion having a mean particle size of 9.7 ⁇ m and a solids content of 43.6% was obtained.
  • Water phase 850 g of water 138 g of a 50% strength by weight, alkali-stabilized silica sol (specific surface area approx.
  • Feed 2 35.5 g of a 1% strength by weight aqueous ascorbic acid solution
  • the aqueous phase was initially introduced at 40 ° C., into which the oil phase was added and dispersed for 40 minutes with a high-speed dissolver stirrer (disc diameter 5 cm) at 3500 rpm.
  • the emulsion was heated with stirring with an anchor raker in 60 minutes at 70 0 C, within a further 60 minutes at 85 0 C and held at 85 0 C for one hour.
  • Feed 1 was added to the resulting microcapsule dispersion with stirring.
  • Feed 2 was metered in with stirring over 90 minutes while being cooled to room temperature. Then it was neutralized with sodium hydroxide solution.
  • a microcapsule dispersion having an average particle size of 8.4 ⁇ m and a solids content of 43.6% was obtained.
  • alkali-stabilized silica sol (average particle size about 30 nm) 25 g of a 1% strength by weight aqueous solution of methylhydroxyethylcellulose
  • a microcapsule dispersion having a mean particle size of 4.3 ⁇ m and a solids content of 43.2% was obtained.
  • Example 5 The procedure was as in Example 3 with the difference that the following oil phase was used:
  • a microcapsule dispersion having an average particle size of 8.7 ⁇ m and a solids content of 44.0% was obtained.
  • Hydrocarbons A microcapsule dispersion having a mean particle size of 9.7 ⁇ m and a solids content of 42.2% was obtained.
  • the recipe used corresponded to ordinary ready-mix concrete and contained 337 kg Ashgrove cement, 739 kg sand, 2370 kg aggregate and 172 kg water. These quantities refer to a m 3 concrete block.
  • the not inventive example 1 b shows that the entry of air bubbles leads to a good freeze-thaw stability, but leads to a poor compressive strength of the concrete block.
  • the concrete block according to the invention has both a good freeze-thaw stability and good compressive strength.
  • microcapsule dispersions obtained according to Examples 2 to 6 can be used to produce concrete blocks with good freeze-thaw stabilities and good compressive strength analogously to ready-mixed concrete.
  • Concrete mixture 2a, 2b and 2c Concrete mixture 2a (basic recipe - not according to the invention)
  • a self-compacting concrete (SVB) consisting of 417 kg Ashgrove cement, 830 kg sand, 2166 kg aggregate and 146 kg water was produced.
  • SVB self-compacting concrete
  • 3.8 kg were Glenium ® 7500 (polycarboxylate; BASF Aktiengesellschaft) were used. These quantities refer to a m 3 concrete block.
  • microcapsule dispersions obtained according to Examples 2 to 6 concrete blocks with good freeze-thaw stabilities and good compressive strength can be produced analogously from self-compacting concrete.
  • a fly ash-containing ready-mixed concrete was produced from 268 kg Ashgrove cement, 67 kg fly ash, 745 kg sand, 2400 kg aggregate and 151 kg water. These quantities refer to a m 3 concrete block.
  • Concrete mix 3c (according to invention) Notwithstanding the basic formulation were 16.6 kg microcapsule dispersion of Example 1 dosed at a m 3 of concrete, in that a corresponding volume of this amount of water was replaced.
  • microcapsule dispersions obtained according to Examples 2 to 6 concrete blocks with good freeze-thaw stabilities and good compressive strength can be produced analogously from fly ash-containing transport concrete.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Nanotechnology (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

L'invention concerne une nouvelle utilisation de microcapsules qui ont une paroi en polymère et dont le noyau est formé par une substance lipophile ayant un point de fusion ≤120 °C et un point d'ébullition ≥100 °C, en tant qu'additifs de stabilité au gel-dégel dans des mélanges de matériaux de construction à prise hydraulique.
PCT/EP2008/062716 2007-09-25 2008-09-24 Mélanges de matériaux de construction à prise hydraulique contenant des substances lipophiles microencapsulées WO2009040359A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08804629A EP2203397A1 (fr) 2007-09-25 2008-09-24 Mélanges de matériaux de construction à prise hydraulique contenant des substances lipophiles microencapsulées

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07117126.8 2007-09-25
EP07117126 2007-09-25

Publications (1)

Publication Number Publication Date
WO2009040359A1 true WO2009040359A1 (fr) 2009-04-02

Family

ID=40350200

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/062716 WO2009040359A1 (fr) 2007-09-25 2008-09-24 Mélanges de matériaux de construction à prise hydraulique contenant des substances lipophiles microencapsulées

Country Status (2)

Country Link
EP (1) EP2203397A1 (fr)
WO (1) WO2009040359A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2575790A1 (fr) * 2010-06-07 2013-04-10 Syngenta Participations AG Composition chimique stabilisée
US8535558B2 (en) 2009-07-10 2013-09-17 Basf Se Microcapsules with polyvinyl monomers as crosslinker
WO2013156590A1 (fr) * 2012-04-19 2013-10-24 Construction Research & Technology Gmbh Adjuvant et procédé conférant à des compositions cimentaires une résistance aux cycles gel-dégel et à l'écaillage
US9333685B2 (en) 2012-04-19 2016-05-10 AkzoNobel Chemicals International B.V. Apparatus and system for expanding expandable polymeric microspheres
CN109020454A (zh) * 2018-10-16 2018-12-18 佛山市宝粤美科技有限公司 水泥基保温材料的生产方法
CN109020308A (zh) * 2018-10-16 2018-12-18 佛山市宝粤美科技有限公司 透水混凝土的生产方法
CN109020357A (zh) * 2018-10-16 2018-12-18 佛山市宝粤美科技有限公司 防结冰水泥基材料的生产方法
US10640422B2 (en) 2013-12-06 2020-05-05 Construction Research & Technology Gmbh Method of manufacturing cementitious compositions
US10988416B2 (en) * 2018-04-23 2021-04-27 United States Gypsum Company Colloidal vesicles for use as dedusting agents in construction panels

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19749731A1 (de) * 1997-11-11 1999-05-12 Basf Ag Verwendung von Mikrokapseln als Latentwärmespeicher
WO2003016650A1 (fr) * 2001-08-16 2003-02-27 Basf Aktiengesellschaft Utilisation de microcapsules dans des plaques de platre
EP1321182A1 (fr) * 2001-12-20 2003-06-25 Basf Aktiengesellschaft Microcapsules
DE102004005912A1 (de) * 2004-02-05 2005-08-25 Basf Ag Schallabsorbierende Formkörper
WO2006092439A1 (fr) * 2005-03-04 2006-09-08 Basf Aktiengesellschaft Poudre constituee de microcapsules

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19749731A1 (de) * 1997-11-11 1999-05-12 Basf Ag Verwendung von Mikrokapseln als Latentwärmespeicher
WO2003016650A1 (fr) * 2001-08-16 2003-02-27 Basf Aktiengesellschaft Utilisation de microcapsules dans des plaques de platre
EP1321182A1 (fr) * 2001-12-20 2003-06-25 Basf Aktiengesellschaft Microcapsules
DE102004005912A1 (de) * 2004-02-05 2005-08-25 Basf Ag Schallabsorbierende Formkörper
WO2006092439A1 (fr) * 2005-03-04 2006-09-08 Basf Aktiengesellschaft Poudre constituee de microcapsules

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8535558B2 (en) 2009-07-10 2013-09-17 Basf Se Microcapsules with polyvinyl monomers as crosslinker
US10314304B2 (en) 2010-06-07 2019-06-11 Sygenta Participations Ag Stabilized chemical composition
EP2575790A4 (fr) * 2010-06-07 2013-11-13 Syngenta Participations Ag Composition chimique stabilisée
US11503827B2 (en) 2010-06-07 2022-11-22 Syngenta Participations Ag Stabilized chemical composition
EP2575790A1 (fr) * 2010-06-07 2013-04-10 Syngenta Participations AG Composition chimique stabilisée
WO2013156590A1 (fr) * 2012-04-19 2013-10-24 Construction Research & Technology Gmbh Adjuvant et procédé conférant à des compositions cimentaires une résistance aux cycles gel-dégel et à l'écaillage
CN104244998A (zh) * 2012-04-19 2014-12-24 建筑研究和技术有限公司 用于水泥组合物的抗冻融损伤和抗剥落损伤的掺加剂和方法
US9150452B2 (en) 2012-04-19 2015-10-06 Construction Research & Technology, Gmbh Method for manufacturing a cementitious composition
US9333685B2 (en) 2012-04-19 2016-05-10 AkzoNobel Chemicals International B.V. Apparatus and system for expanding expandable polymeric microspheres
US9365453B2 (en) 2012-04-19 2016-06-14 Construction Research & Technology Gmbh Admixture and method for freeze-thaw damage resistance and scaling damage resistance of cementitious compositions
US9586348B2 (en) 2012-04-19 2017-03-07 Construction Research & Technology Gmbh Apparatus and system for expanding expandable polymeric microspheres
US10774000B2 (en) 2012-04-19 2020-09-15 Construction Research & Technology Gmbh Admixture and method for freeze-thaw damage resistance and scaling damage resistance of cementitious compositions
US10865142B2 (en) 2013-12-06 2020-12-15 Construction Research & Technology Gmbh Method of making cementitious compositions
US10640422B2 (en) 2013-12-06 2020-05-05 Construction Research & Technology Gmbh Method of manufacturing cementitious compositions
US10988416B2 (en) * 2018-04-23 2021-04-27 United States Gypsum Company Colloidal vesicles for use as dedusting agents in construction panels
CN109020357A (zh) * 2018-10-16 2018-12-18 佛山市宝粤美科技有限公司 防结冰水泥基材料的生产方法
CN109020308A (zh) * 2018-10-16 2018-12-18 佛山市宝粤美科技有限公司 透水混凝土的生产方法
CN109020308B (zh) * 2018-10-16 2021-05-04 成都冶兴润达新型建材有限公司 透水混凝土的生产方法
CN109020454B (zh) * 2018-10-16 2021-07-02 建始县泰丰水泥有限责任公司 水泥基保温材料的生产方法
CN109020357B (zh) * 2018-10-16 2021-11-30 佛山市宝粤美科技有限公司 防结冰水泥基材料的生产方法
CN109020454A (zh) * 2018-10-16 2018-12-18 佛山市宝粤美科技有限公司 水泥基保温材料的生产方法

Also Published As

Publication number Publication date
EP2203397A1 (fr) 2010-07-07

Similar Documents

Publication Publication Date Title
EP2043773B1 (fr) Microcapsules modifiées par polyélectrolytes
EP2099557B1 (fr) Microcapsules
EP1858635B1 (fr) Poudre constituee de microcapsules
EP1029018B1 (fr) Utilisation de microcapsules en tant qu'accumulateurs de chaleur latente
WO2009040359A1 (fr) Mélanges de matériaux de construction à prise hydraulique contenant des substances lipophiles microencapsulées
EP1321182B1 (fr) Microcapsules
EP1421243B1 (fr) Utilisation de microcapsules dans des plaques de platre
EP1781752B1 (fr) Preparation de microcapsules a grosses particules
EP1362900B1 (fr) Equipment ignifuge pour les articles contenant des materiaux organiques d'accumulation de chaleur latente
EP2234712B1 (fr) Procédé de production de microcapsules
EP2451849B1 (fr) Microcapsules comprenant des monomères polyvinyle comme agents réticulants
WO2008046839A1 (fr) Microcapsules
EP1841517A1 (fr) Preparation de microcapsules a grosses particules
DE102007055813A1 (de) Thermisch zerstörbare Mikrokapseln
EP2483491A1 (fr) Plaque de plâtre contenant des matériaux accumulateurs de chaleur latente micro-encapsulés
DE19954772A1 (de) Verwendung von siliciumorganischen Mikrokapseln als Latentwärmespeicher
DE102004005912A1 (de) Schallabsorbierende Formkörper

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08804629

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2008804629

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2008804629

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载