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WO2017016971A1 - Procédé de production d'une composition de microcapsules - Google Patents

Procédé de production d'une composition de microcapsules Download PDF

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Publication number
WO2017016971A1
WO2017016971A1 PCT/EP2016/067389 EP2016067389W WO2017016971A1 WO 2017016971 A1 WO2017016971 A1 WO 2017016971A1 EP 2016067389 W EP2016067389 W EP 2016067389W WO 2017016971 A1 WO2017016971 A1 WO 2017016971A1
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WO
WIPO (PCT)
Prior art keywords
monomers
microcapsule
microcapsules
weight
microcapsule composition
Prior art date
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PCT/EP2016/067389
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German (de)
English (en)
Inventor
Roland Hinrich STAFF
Marco Schmidt
Kresimir Cule
Britta Katz
Achim PIESCH
Jutta BRUST
Original Assignee
Basf Se
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Publication of WO2017016971A1 publication Critical patent/WO2017016971A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043—Drying and spraying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
    • F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D2020/0065—Details, e.g. particular heat storage tanks, auxiliary members within tanks
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/04—Coatings; Surface treatments hydrophobic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to a process for the preparation of a microcapsule composition comprising microcapsules having an average particle diameter of D [4,3] of 0.5 to 5 ⁇ comprising the steps
  • monomers I selected from C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid, acrylic acid and methacrylic acid,
  • microcapsules by means of polymerizing the monomers in the oil-in-water emulsion obtained in step a) and
  • the present invention relates to the microcapsule composition obtainable by this process and its use for the production of thermoplastic moldings.
  • PCMs phase change materials
  • the functioning of the PCMs is based on the conversion enthalpy occurring during the solid / liquid phase transition, which means an energy absorption or energy release to the environment, so that they are used for the storage of heat as so-called latent heat storage.
  • Another effect is described in WO2009 / 080232. The difference of
  • thermotropic plastics are suitable for sun protection.
  • Muehling Seeboth, Haeusler, Ruhmann, Potechius, cousin; Solar Energy Materials & Solar Cells "93 (2009) 1510-1517, describes microcapsules based on crosslinked Methyl methacrylate, which are obtained by means of miniemulsion polymerization with polyvinyl alcohol as a nonionic surfactant.
  • the microcapsules described herein have a thermotropic effect embedded in a polymeric matrix.
  • microcapsules have a broad particle distribution.
  • WO 2012/069976 teaches the preparation of a thermoplastic molding composition containing microencapsulated latent heat storage materials. According to this doctrine, the
  • Microcapsules in order to minimize the thermal load, fed late in the plasticizing zone of the extruder.
  • the polymer blends obtainable in this way can be used to produce fibers, films and shaped articles.
  • thermoplastic polymer If one wants to process a microcapsule powder together with a thermoplastic polymer, an important requirement is the uniform distribution of the microcapsules in thermoplastics.
  • WO 2014/127951 teaches that the use of emulsion polymers as spray aids leads to aggregates of microcapsules which can then be separated in the melt of the thermoplastic polymer.
  • the microcapsules used for this purpose have an average particle size of 5 ⁇ .
  • Microcapsules with average particle diameters ⁇ 2 ⁇ m are generally known and are described, for example, in WO 01/54809. According to this teaching, they are prepared by means of polyvinyl alcohol as a protective colloid.
  • the microcapsules obtained according to this teaching are tried to be spray-dried and extruded with a thermoplastic polymer, it is found that the extrudates obtained thereafter hardly receive isolated microcapsules. Therefore, the object of the present invention to provide a method which makes it possible to produce microcapsules of average particle size D [4,3] from 0.7 to 5 ⁇ whose dispersion can be spray-dried and the aggregates obtained thereafter process well in with a thermoplastic polymer and let it separate uniformly in the thermoplastic polymer.
  • the moldings produced in this way should show a good thermotropic effect.
  • thermoplastic moldings containing microcapsules which have a temperature-dependent change in the radiation permeability. Accordingly, the process defined at the beginning, as well as the microcapsule composition obtainable hereinafter, has been found, its use for the production of thermoplastic moldings and the resulting thermoplastic moldings.
  • microcapsule composition prepared according to the invention comprises microcapsules (primary particles) having an average particle diameter D [4,3] of 0.5 to 5 ⁇ m, preferably of 0.7 to 2 ⁇ m (volume-weighted average, determined by means of light scattering).
  • the microcapsules are composed of a capsule core of hydrophobic core material and a capsule wall polymer.
  • the capsule core consists predominantly, to more than 90 wt .-%, of hydrophobic core material.
  • the capsule core can be both solid and liquid, depending on the temperature.
  • 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. Since the microcapsules are prepared by free-radical polymerization in an oil-in-water emulsion, an aqueous microcapsule dispersion is obtained. If this microcapsule dispersion is dehydrated, for example by means of spray drying, then aggregates (secondary particles) of the microcapsules are obtained. Such secondary particles are often referred to as granules or agglomerate.
  • the shape of the aggregates can be uneven or spherical or egg-shaped.
  • an inorganic protective colloid is used. It has been observed that this protective colloid is also part of the capsule wall. In general, the surface of the capsule wall polymer in particular has the protective colloid. Thus, up to 20% by weight protective colloid, based on the total weight of the microcapsules, may be part of the microcapsule.
  • Hydrophobic core materials are, for example, aliphatic hydrocarbon compounds such as saturated or unsaturated C 10 -C 40 -hydrocarbons which are branched or preferably linear, aromatic hydrocarbon compounds, saturated or unsaturated C 6 -C 30 -fatty acids, fatty alcohols and the so-called oxo alcohols which are obtained by hydroformylation of ⁇ - Olefins and further reactions are obtained, ethers of fatty alcohols, C6-C3o-fatty amines, esters such as Ci-Cio-alkyl esters of fatty acids such as propyl palmitate, methyl stearate or methyl palmitate and preferably their eutectic mixtures or methyl cinnamate, natural and synthetic see waxes and halogenated hydrocarbons , as listed in WO 2009/077525, the disclosure of which is expressly incorporated by reference.
  • aliphatic hydrocarbon compounds such as saturated or unsaturated C 10 -C 40 -hydrocarbons which are
  • Suitable substances may be mentioned by way of example:
  • aliphatic hydrocarbon compounds such as saturated or unsaturated
  • Cio-C4o hydrocarbons which are branched or preferably linear, such as n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-eicosane, n-heneicosane, n-docosan, n-tricosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane and cyclic hydrocarbons, for example cyclohexane, cyclooctane, cyclodecane;
  • aromatic hydrocarbon compounds such as benzene, naphthalene, biphenyl, o- or n-terphenyl, C 1 -C 4 -alkyl-substituted aromatic hydrocarbons such as dodecylbenzene, tetradecylbenzene, hexadecylbenzene, hexylnaphthalene or decylnaphthalene;
  • saturated or unsaturated C6-C30 fatty acids such as lauric, stearic, oleic or behenic acid, preferably eutectic mixtures of decanoic acid with e.g. Myristic, palmitic or lauric acid;
  • Fatty alcohols such as lauryl, stearyl, oleyl, myristyl, cetyl alcohol, mixtures such as coconut fatty alcohol and the so-called oxo alcohols, which are obtained by hydroformylation of ⁇ -olefins and further reactions;
  • C6-C3o fatty amines such as decylamine, dodecylamine, tetradecylamine or hexadecylamine
  • Esters such as C 1 -C 10 -alkyl esters of fatty acids such as propyl palmitate, methyl stearate or methyl palmitate, and preferably their eutectic mixtures or methyl cinnamate;
  • waxes such as montanic acid waxes, montan ester waxes,
  • Carnauba wax polyethylene wax, oxidized waxes, polyvinyl ether wax, ethylene vinyl acetate wax or Fischer-Tropsch hard waxes;
  • halogenated hydrocarbons such as chlorinated paraffin, bromoctadecane, bromopentadecane, bromononadecane, bromeicosane, bromodocosane.
  • n-alkanes n-alkanes having a purity of greater than 90% or of alkane mixtures, as obtained as a technical distillate and are commercially available as such.
  • Preferred hydrophobic core materials are aliphatic hydrocarbons, particularly preferably those enumerated above by way of example. In particular, aliphatic hydrocarbons having 14 to 20 carbon atoms and mixtures thereof are preferred.
  • soluble compounds may be added to the hydrophobic core material so as to prevent the crystallization retardation which sometimes occurs with the nonpolar core materials. It is advantageous to use, as described in US Pat. No. 5,456,852, compounds having a melting point 20 to 120 K higher than the actual core material. Suitable compounds are the fatty acids mentioned above as hydrophobic core materials, fatty alcohols, fatty amides and aliphatic hydrocarbon compounds and chlorinated paraffin. They are added in amounts of from 0.1 to 10% by weight, based on the capsule core. As hydrocarbon compounds having a melting point of 20 to 120 K, suitable compounds include Sasolwax 6805, British Wax 1357 and, as fatty acid, stearic acid by way of example.
  • the polymers of the capsule wall generally contain at least 40% by weight, preferably at least 50% by weight, in particular at least 55% by weight, very preferably at least 70% by weight and in general up to 90% by weight. %, preferably at most 85 Wt .-%, in particular at most 85 wt .-% and most preferably at most 80 wt .-%, based on the total weight of the monomers, of at least one monomer selected from Ci-C24-alkyl esters of acrylic and / or methacrylic acid, acrylic acid and Methacrylic acid (monomers I), copolymerized.
  • the polymers of the capsule wall contain at least 10 wt .-%, preferably at least 15 wt .-%, preferably at least 20 wt .-% and generally at most 60 wt .-% and in a preferred form at most 50 wt .-%, in particular at most
  • the polymers of the capsule wall preferably comprise, as monomers II, monomers having three, four or more ethylenically unsaturated radicals in copolymerized form.
  • 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 and the unsaturated C 3 - and C 4 -carboxylic acids, such as acrylic acid and methacrylic acid.
  • Suitable monomers I are isopropyl, isobutyl, sec-butyl and tert-butyl acrylate and the corresponding methacrylates, and particularly preferred methyl, ethyl, n-propyl and n-butyl acrylate and the corresponding methacrylates.
  • the methacrylates and methacrylic acid are preferred.
  • Suitable monomers II are ethylenically unsaturated monomers having two, three, four or more ethylenically unsaturated radicals.
  • Ethylenically unsaturated monomers having two, three, four or more ethylenically unsaturated radicals are understood as meaning those which have non-conjugated ethylenic double bonds. They cause a crosslinking of the capsule wall during the polymerization.
  • One or more monomers having two non-conjugated ethylenic double bonds (divinyl monomers) and / or one or more monomers having three, four or more non-conjugated ethylenic double bonds may be copolymerized.
  • Low solubility is to be understood as meaning a solubility of less than 60 g / l at 20 ° C.
  • 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. Particular preference is given to propanediol, butanediol, pentanediol and hexanediol diacrylate and the corresponding methacrylates.
  • Preferred monomers having three, four or more nonconjugated ethylenic double bonds are the esters of polyhydric alcohols with acrylic acid and / or methacrylic acid, furthermore the allyl and vinyl ethers of these polyhydric alcohols, trivinylbenzene and trivinylcyclohexane.
  • trimethylol and pentaerythritol are mentioned as polyhydric alcohols.
  • pentaerythritol tetraacrylate is generally present in industrial blends mixed with pentaerythritol triacrylate and minor amounts of oligomerization products.
  • those combinations are preferred in which at least 80 wt .-% based on the monomer II, one or more monomers having three, four or more ethylenically unsaturated radicals.
  • 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 .alpha.-methylstyrene and particularly preferred monomers itaconic acid, vinylphosphonic acid, maleic anhydride, 2-hydroxyethyl acrylate and methacrylate , Acrylamido-2-methylpropanesulfonic acid, methacrylonitrile, acrylonitrile, methacrylamide, N-vinylpyrrolidone, N-methylolacrylamide, N-methylol-methacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
  • microcapsules are selected whose capsule wall is built up
  • microcapsules are selected whose capsule wall is built up
  • Ci-C24-alkyl esters of acrylic and / or methacrylic acid (monomers 30 to 50 wt .-% of one or more ethylenically unsaturated monomers having three, four or more ethylenically unsaturated radicals (monomers II), and
  • microcapsules used according to the invention can be prepared by a so-called in situ polymerization.
  • the principle of microcapsule formation is based on preparing from the monomers, radical initiator, inorganic protective colloid, polyalkylene glycol ethers and the hydrophobic core material to be encapsulated an oil-in-water emulsion in which the monomers and the hydrophobic core material are in the form of a disperse phase.
  • the polymerization of the monomers is initiated by heating and optionally controlled by further increase in temperature, wherein the resulting polymers form the capsule wall, which encloses the hydrophobic core material.
  • radical starter is part of the oil phase of the oil-in-water emulsion and there triggers the polymerization.
  • Preferred free-radical initiators are tert-butyl peroxoneodecanoate, tert-amyl peroxypivalate, dilauroyl peroxide, tert-amyl peroxy-2-ethylhexanoate, 2,2'-azobis (2,4-dimethyl) valeronitrile, 2,2'-azobis (2 methyl butyronitrile), dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and cumene hydroperoxide.
  • radical initiators are di (3,5,5-trimethylhexanoyl) peroxide, 4,4'-azobisisobutyronitrile, tert-butyl perpivalate, dilauroyl peroxide, tert-butyl peroxoneodecanoate and dimethyl 2,2-azobisisobutyrate. These have a half-life of 10 hours in a temperature range of 30 to 100 ° C.
  • the microcapsules are prepared in the presence of at least one inorganic protective colloid.
  • Inorganic protective colloids are inorganic solid particles, so-called Pickering systems.
  • Pickering systems can consist of the solid particles alone or in addition of auxiliaries.
  • auxiliaries improve the dispersibility of the inorganic solid particles or the wetting of the inorganic solid particles by the oil phase.
  • the mode of action and its use is described in EP-A-1 029 018 and EP-A-1 321 182, to the contents of which reference is expressly made.
  • 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. Particular preference is given to SiO 2 -based silicas, magnesium pyrophosphate and tricalcium phosphate.
  • Suitable SiO 2 -based protective colloids are finely divided silicas. They 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 protective colloid, it is advantageous if the pH of the oil-in-water emulsion is adjusted to pH 2 to 7 with an acid. Preferred colloidal dispersions of silica at pH 9.3 have a specific surface area in the range of 70 to 90 m 2 / g.
  • SiO 2 -based protective colloids preference is given to highly disperse silicas whose mean particle diameters are in the range from 40 to 150 nm at pH values in the range from 8 to 11. Examples include Levasil® ® 50/50 (HC Starck), Köstrosol ® 3550 (CWK Bad Köstritz), and Bindzil ® mentioned 50/80 (Akzo Nobel Chemicals).
  • SiO 2 -based protective colloids are highly disperse silicas whose average particle diameters are in the range from 5 to 40 nm at pH values in the range from 8 to 11.
  • One example is Ludox ® mentioned HS-40 (Grace Davison).
  • the inorganic protective colloid is preferably present in an amount of 10 to 30,
  • polyalkylene glycol ether is added according to the invention.
  • Polyalkylene glycol ethers are nonionic surfactants of a C6 to C3o fatty alcohol and a polyethylene glycol or polypropylene glycol.
  • Preferred aliphatic, primary alcohols, so-called fatty alcohols are 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-dodecanol (lauryl alcohol), 1-tetradecanol (myristyl alcohol), 1-hexadecanol (cetyl alcohol), 1-heptade- canol (margaryl alcohol), 1-octadecanol (stearyl alcohol), 1-eicosanol (arachidyl alcohol), 1-doscosanol (behenyl alcohol), 1-tetracosanol (lignoceryl alcohol), 1-hexacosanol (ceryl alcohol), 1-octacosanol (montanyl alcohol), 1 Triacontanol (melissy
  • the number of ethoxylation or propoxylation units is generally from 1 to 100. Particular preference is given to ethoxylated hexadecanols having an average of from 10 to 80 ethylene oxide units, very particularly preferably ethoxylated hexane-cananols having on average from 18 to 80 ethylene oxide units.
  • Lutensol® AT25 BASF SE
  • the HLB values refer to Griffin's HLB scale whose maximum value is 20.
  • polyoxyethylene (10) cetyl ether examples which may be mentioned are polyoxyethylene (10) cetyl ether, polyoxyethylene (10) stearyl ether, polyoxyethylene (10) oleyl ether, polyoxyethylene (23) lauryl ether, polyoxyethylene (20) cetyl ether, polyoxyethylene (25) cetyl stearyl ether,
  • the polyalkylene glycol ether is preferably used in an amount of 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-%, based on the sum of hydrophobic core materials and monomers.
  • the polyalkylene glycol ether can be added together with the inorganic protective colloid or individually to the mixture. It is preferably added to the water phase.
  • step b) The polymerization of the monomers (step b) in the oil-in-water emulsion obtained in step a) is generally known and described, for example, in DE-A-10 139 171 and application WO 201 1/004006 and WO 2012/1 10443 to which reference is expressly made.
  • microcapsules primary particles
  • D [4,3] average particle diameter of D [4,3] of from 0.5 to 5 ⁇ m
  • the present invention relates to the microcapsule compositions thus obtainable. Furthermore, it relates to microcapsule compositions containing microcapsules and water, such as are obtainable, for example, according to the above-described method as an aqueous dispersion. Furthermore, the present invention relates to microcapsule compositions which are present as powders. This powdery microcapsule composition is obtainable by dehydrating the microcapsule dispersion obtained from b). By dewatering, it is to be understood below that the microcapsule composition has a water content of ⁇ 5% by weight, preferably ⁇ 3% by weight, based on the weight of the microcapsule composition (determined by means of Karl Fischer titration).
  • the dehydration can be carried out by methods known to the person skilled in the art, for example by means of spray drying, freeze drying or drying in an oven. Preference is given to a process for preparing the microcapsule composition in which the dehydration of the microcapsule dispersion obtained from b) takes place by means of spray-drying.
  • the spray drying of the microcapsule dispersion can be carried out in the usual way.
  • the procedure is that the inlet temperature of the drying gas, usually nitrogen or air, in the range of 100 to 200 ° C, preferably 120 to 160 ° C, and the starting temperature of the drying gas in the range of 30 to 90 ° C, preferably 60 to 80 ° C is located.
  • the spraying of the aqueous microcapsule dispersion in the drying gas stream can take place, for example, by means of single-component or multi-component nozzles or via a rotating disk.
  • the droplet size on exit is chosen so as to produce a microcapsule powder having the desired particle diameter.
  • the person skilled in the art will choose the diameter of the nozzle and the precursor pressure of the material stream. The higher the form, the smaller the droplets are produced.
  • the microcapsule dispersion is fed in the range of 2-200 bar.
  • a single-fluid nozzle with swirl generator is used. By selecting the swirl generator, droplet size and spray angle can be additionally influenced.
  • single-substance nozzles from Delavan, which have a typical structure consisting of swirl chamber, which influences the spray angle, and perforated plate, which influences the throughput.
  • the deposition of the powdered microcapsule composition is usually carried out using cyclones or filter separators.
  • the sprayed aqueous microcapsule dispersion and the drying gas stream are preferably conducted in parallel.
  • the drying gas stream is blown in cocurrent with the microcapsule dispersion from above into the tower.
  • Spray-drying fluidized-bed drying is preferred because it results in a micro-capsule composition having a lower fines content.
  • a spray tower for example, dryers Anhydro, Miro or Nubilosa can be used, the tower heights of 12-30 meters and widths of 3 to 8 meters have.
  • the throughput of drying gas is typically in the range of 20-30 t h for such spray towers.
  • the throughput of microcapsule dispersion is then usually at 1 to 1, 5 t / h.
  • spraying aids are added for spray-drying in order to facilitate spray-drying or to adjust certain powder properties.
  • an emulsion polymer in the form of an aqueous dispersion is used as spraying assistant, the emulsion polymer
  • esters of acrylic and / or methacrylic acid with 1 to 12 carbon atoms aufwei send alkanols and / or styrene, or
  • the total amount of emulsion polymer (calculated as solids), which is added to the aqueous microcapsule dispersion before or during, but especially before spray drying, for example, 1 to 40 parts by weight, often 1 to 25 parts by weight and often 5 to 25 wt ., Each based on 100 parts by weight of microcapsules.
  • Emulsion polymers are familiar to the person skilled in the art and are prepared, for example, in the form of an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers. This method has been described many times and is therefore well known to the person skilled in the art.
  • Aqueous polymer dispersions are also commercially available, eg under the brands ACRONAL® ®, STYRONAL® ®, Butofan ®, Styrofan ® and Kollicoat ® of BASF SE, Ludwigshafen, Germany, VINNOFIL ® and VINNAPAS ® from. Wacker Chemie GmbH, Burghausen, and RHODIMAX ® from. Rhodia SA
  • the preferred aqueous vinyl acetate-ethylene dispersions have an ethylene content of from 5 to 40% by weight, based on the polymer. If other monomers are used in addition to vinyl acetate and ethylene, the polymer advantageously has a vinyl acetate content of more than 45% by weight.
  • Suitable monomers are olefinically unsaturated monomers, such as vinyl ethers of straight-chain or branched carboxylic acids having 3-18 C atoms, acrylic, methacrylic, maleic or fumaric acid esters of aliphatic alcohols having 1-18 C atoms, vinyl chloride, furthermore isobutylene or higher ⁇ -olefins with 4 to 12 C atoms.
  • vinyl ethers of straight-chain or branched carboxylic acids having 3-18 C atoms acrylic, methacrylic, maleic or fumaric acid esters of aliphatic alcohols having 1-18 C atoms, vinyl chloride, furthermore isobutylene or higher ⁇ -olefins with 4 to 12 C atoms.
  • vinyl acetate and ethylene are suitable monomer combinations z.
  • vinyl acetate / vinyl pivalate / E-thy-len vinyl acetate 2-ethylhexanoic acid vinyl ester / ethylene, vinyl acetate / methyl methacrylate ethylene and vinyl acetate / vinyl chloride / ethylene, from the group of so-called terpolymers.
  • Advantageous are monomer combinations with a minimum film-forming temperature of the corresponding dispersions of> 16 ° C.
  • stabilizing monomers such as the sodium salt of vinylsulfonic acid, monomers containing carboxyl groups, such as acrylic, methacrylic, crotonic or itaconic acid or monoesters of maleic acid, whose alcohol component has 1 to 18 carbon atoms, to be incorporated in copolymerized form, in a concentration of up to 5% by weight, based on the emulsion polymer.
  • the aqueous emulsion polymer dispersion can be used directly as a spray aid in the form of its aqueous dispersion resulting from the synthesis.
  • they are used as 45 to 65 wt .-% dispersions.
  • an emulsion polymer described above is used in the form of an aqueous dispersion as a spray aid, this is preferably done with the addition of a release agent.
  • Suitable release agents are those which are usually used in the isolation of these emulsion polymers as a solid, such as kaolin or silica.
  • the powdery microcapsule compositions obtained by spray-drying are particles which usually consist of 2 to several thousand individual capsules which are together are connected.
  • the powder particles (secondary particles) are aggregates of microcapsules (primary particles).
  • Preference is given to average particle diameter of the microcapsule powder whose particle diameter is at least twice the primary particle.
  • Particle diameters D [4,3] of the powder particles up to 200 ⁇ m, in particular up to 150 ⁇ m, are preferred.
  • Particular preference is given to mean particle diameters of the powder particles with D [4,3] of 1 to 50 ⁇ m, in particular of 5 to 20 ⁇ m. Larger mean particle diameters are possible, but can be singularly worse when extruded in moldings usually. Similarly, smaller average particle diameters are possible, but these tend to dust more.
  • microcapsule compositions of the invention are non-dusting powders. They are further distinguished by the fact that they can be incorporated advantageously into thermoplastic polymers and thereby isolated.
  • microcapsule compositions of the invention can be incorporated advantageously into thermoplastic polymers.
  • the microcapsule compositions according to the invention are particularly preferably incorporated into thermoplastic polymers in an extruder or in an injection molding machine for the production of thermoplastic moldings. If the melt-processable molding material is not to be obtained as granules, but is to be used further directly, also the further processing in the hot state or the direct extrusion of plates, films, pipes and profiles or the direct production of plastic components is advantageous.
  • film is often used by a person skilled in the art synonymous with film.
  • the particulate microcapsule compositions can be processed advantageously. It is a good, uniform distribution of the individual microcapsules in the thermoplastic polymer to observe, since the preferably used emulsion polymer of the composition in the thermoplastic polymer evenly distributed and thus the microcapsules are isolated.
  • thermoplastic materials in which the microcapsule compositions according to the invention can be incorporated are:
  • Polyolefins such as polyethylene (PE) and polypropylene (PP),
  • Styrene polymers such as polystyrene (impact-resistant or not impact-modified),
  • ABS acrylonitrile-butadiene-styrene
  • ASA acrylonitrile-styrene-acrylate
  • MABS transparent ABS containing methacrylate units
  • SBS Styrene-butadiene block copolymers
  • S-TPE thermoplastic elastomers based on styrene
  • Polyesters such as polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG) and polybutylene terephthalate (PBT),
  • thermoplastic polyurethanes TPU
  • PIB Polyisobutylene
  • the thermoplastic polymer is a polyolefin, polymethyl methacrylate, polyvinyl butyral or polyolefin copolymer such as ethylene-vinyl acetate copolymers.
  • ethylene-vinyl acetate copolymers are preferred.
  • thermoplastic polymer With the microcapsules obtained according to the invention, the properties of a thermoplastic polymer can be modified. Utilized is the solid-liquid phase transition of the hydrophobic core material associated with a change in refractive index.
  • the hydrophobic core material is, depending on the desired temperature at which the radiation transmission is to be changed, chosen so that it has its phase transition at this temperature.
  • one of the two phases of the hydrophobic core material must have a refractive index similar to the thermoplastic polymer of the shaped body. If, for example, shading is desired when the temperature is raised, then the solid phase and the thermoplastic polymer have a similar refractive index. A film made from this is translucent as long as the core material is solid.
  • the hydrophobic core material melts and its refractive index changes. Due to the now different refractive index of thermoplastic polymer and hydrophobic core material, the film becomes cloudier or cloudier than before. This change of radiation transmission can cause heat regulation.
  • irradiation can also be intensified if the liquid phase and the thermoplastic polymer of the shaped body have a similar refractive index.
  • a hydrophobic core material is selected such that the refractive indices have a maximum difference of 0 at a temperature of 25 ° C and the wavelength 589 nm (sodium D-line) of the solid phase of the hydrophobic core material and the thermoplastic polymer , 05 preferably has 0.03, in particular 0.01.
  • the refractive indices of the hydrophobic core materials or of the polymers are usually to be taken from tables or determined by a simple experiment.
  • microcapsule compositions according to the invention are suitable as additives in polymeric moldings or polymeric coating compositions. These are thermoplastic materials.
  • the films according to the invention can be obtained by extrusion through a flat die or preferably as blown films.
  • the films have a good temperature-dependent change in the radiation transmission.
  • the films according to the invention can be used as sunscreen films,
  • the particle diameter of the microcapsule dispersion is determined with a Malvern Mastersizer 2000, Sample Dispersing Unit Hydro 2000S according to a standard measuring method documented in the literature.
  • the value D [4,3] stands for the volume-weighted average.
  • demineralised water (VE demineralized) 175 g of a 40 wt .-% dispersion of a colloidal silica having a particle diameter of 12 nm
  • the water phase was initially introduced at 25.degree. C. and heated to 45.degree. Feeds 1 and 2 were added and the mixture was dispersed for 40 minutes at 45 ° C and 6000 revolutions per minute. After addition of feed 3, the emulsion was heated to a temperature of 67 ° C. over a period of 60 minutes and then heated to a temperature of 90 ° C. over a period of 60 minutes. The mixture was then held at this temperature for 150 minutes, and fed to feed 4. Following was cooled to room temperature. A dispersion having a solids content of 40.1% by weight and a mean particle diameter D [4.3] of 1.10 ⁇ m, determined by means of light scattering, was obtained.
  • Example 2 (according to the invention)
  • microcapsule dispersion was prepared as in Example 1. The resulting microcapsule dispersion was further added after cooling to room temperature:
  • a dispersion having a solids content of 32.2% by weight and a mean particle diameter D [4.3] of 1.75 ⁇ m was obtained, determined by means of light scattering.
  • Example 3 (not according to the invention) water phase
  • the dispersion was then spray-dried to remove the water. A white powder was obtained.
  • microcapsule dispersion was prepared as in Example 1. However, different monomer compositions were used, which are shown in Table 1.
  • aqueous microcapsule dispersion (685.28 g) was 643.27 g Vi- acetate-ethylene dispersion (Vinnapas ® (Fa. Wacker polymer) and eluted with 671, filled 45 g of demineralized water.
  • Vi- acetate-ethylene dispersion Vi- acetate-ethylene dispersion (Vinnapas ® (Fa. Wacker polymer) and eluted with 671, filled 45 g of demineralized water.
  • the dispersion thus obtained was dried to obtain a powder with a laboratory spray dryer (cylinder diameter 250 mm, cylinder length 500 mm).
  • the dispersion was atomized with a two-fluid nozzle (nozzle 1, 4 mm, nozzle pressure 3 bar).
  • the drying gas nitrogen
  • the drying gas had an inlet temperature of 150 ° C and an outlet temperature of 80 ° C.
  • a particulate microcapsule composition (cyclone discharge) was obtained.
  • Particle diameter 1 1, 65 ⁇
  • Example 2 The aqueous microcapsule dispersion obtained from Example 2 was spray-dried directly without further addition. The spray drying was otherwise as described above.
  • a particulate microcapsule composition was obtained.
  • the particles were not agglomerated.
  • the particle diameter was unchanged.
  • the aqueous microcapsule dispersion obtained from Example 3 was spray-dried directly without further addition. The spray drying was otherwise as described above.
  • Example of foil 2 10 parts by weight of the particulate microcapsule composition of Example B1 was added to 90 parts by weight of an ethylene vinyl acetate copolymer (Exxon Mobil - Escorene Ultra UL00014). mixed and refluxed in a mini extruder (DSM Micro 15) at 180 ° C for 3 minutes. Subsequently, the melt is extruded through a 200 ⁇ m nozzle and drawn up manually as a film.
  • Example of foil 2 10 parts by weight of the particulate microcapsule composition of Example B1 was added to 90 parts by weight of an ethylene vinyl acetate copolymer (Exxon Mobil - Escorene Ultra UL00014). mixed and refluxed in a mini extruder (DSM Micro 15) at 180 ° C for 3 minutes. Subsequently, the melt is extruded through a 200 ⁇ m nozzle and drawn up manually as a film.
  • Example of foil 2 10 parts by weight of the particulate microcapsule composition of
  • Example B1 5 parts by weight of the particulate microcapsule composition of Example B1 were mixed with 95 parts by weight of an ethylene vinyl acetate copolymer (Exxon Mobil - Escorene Ultra UL00014) and refluxed in a mini extruder (DSM Micro 15) at 180 ° C. for 3 minutes. Subsequently, the melt is extruded through a 200 ⁇ m nozzle and drawn up manually as a film.
  • an ethylene vinyl acetate copolymer Exxon Mobil - Escorene Ultra UL00014
  • DSM Micro 15 mini extruder
  • Example B3 10 parts by weight of the particulate microcapsule composition of Example B3 was blended with 90 parts by weight of an ethylene vinyl acetate copolymer (Exxon Mobil - Escorene Ultra UL00014) and refluxed in a mini extruder (DSM Micro 15) at 180 ° C for 3 minutes. Subsequently, the melt is extruded through a 200 ⁇ m nozzle and drawn up manually as a film.
  • an ethylene vinyl acetate copolymer Exxon Mobil - Escorene Ultra UL00014
  • DSM Micro 15 mini extruder
  • the resulting film is broken up in liquid nitrogen and the fracture edge is examined with the aid of a scanning electron microscope.
  • the degree of singulation and distribution of the capsules in the polymer film is detected optically.
  • Both film 1 and film 2 showed isolated microcapsules.
  • Only aggregates of the capsules were present in film 3.
  • Film 1 and film 2 had at a temperature of 40 ° C a significantly higher compared to 20 ° C turbidity. There was no difference in film 3, which is due to the lack of separation of the capsules.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

La présente invention concerne un procédé de production d'une composition de microcapsules contenant des microcapsules présentant un diamètre moyen de particules D[4,3] de 0,5 à 5 μηη, le procédé comprenant les étapes suivantes : a) la production d'une émulsion huile dans eau contenant une composition monomère, un matériau central hydrophobe, de l'eau, un initiateur de radicaux, un colloïde protecteur inorganique et un polyalkylène glycol éther, la composition monomère comprenant 40 à 90 % en poids d'un ou de plusieurs monomères (monomères I) choisis parmi l'alkyle ester C1-C24 de l'acide acrylique et/ou méthacrylique, l'acide acrylique et l'acide méthacrylique, 10 à 60 % en poids d'un ou de plusieurs monomères éthyléniques insaturés qui présentent deux, trois, quatre restes éthyléniquement insaturés ou plus, et 0 à 40 % en poids d'un ou de plusieurs autres monomères (monomères III) dans tous les cas par rapport au poids total des monomères, b) la formation des microcapsules par polymérisation des monomères dans l"émulsion huile dans eau obtenue à l'étape a), et c) éventuellement la déshydratation de la dispersion de microcapsules obtenue à l'étape b). L'invention concerne également une composition de microcapsules obtenue par ce procédé, ainsi que son utilisation pour la production de corps moulés thermoplastiques.
PCT/EP2016/067389 2015-07-30 2016-07-21 Procédé de production d'une composition de microcapsules WO2017016971A1 (fr)

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WO2012069976A1 (fr) 2010-11-24 2012-05-31 Basf Se Composition de moulage thermoplastique comprenant un matériau accumulateur de chaleur latente microencapsulé
US20120205576A1 (en) * 2011-02-16 2012-08-16 Basf Se Microcapsules with a paraffin composition as capsule core
WO2012110443A1 (fr) 2011-02-16 2012-08-23 Basf Se Microcapsules à composition de paraffine comme coeur de capsule
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