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WO2013041257A1 - Photopolymérisation d'aérosol - Google Patents

Photopolymérisation d'aérosol Download PDF

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Publication number
WO2013041257A1
WO2013041257A1 PCT/EP2012/062099 EP2012062099W WO2013041257A1 WO 2013041257 A1 WO2013041257 A1 WO 2013041257A1 EP 2012062099 W EP2012062099 W EP 2012062099W WO 2013041257 A1 WO2013041257 A1 WO 2013041257A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
monomer
mma
gas stream
droplets
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.)
Ceased
Application number
PCT/EP2012/062099
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German (de)
English (en)
Inventor
Wolfgang Gerlinger
Michael Wörner
Erlan AKGÜN
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.)
BASF SE
Karlsruher Institut fuer Technologie KIT
Original Assignee
BASF SE
Karlsruher Institut fuer Technologie KIT
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, Karlsruher Institut fuer Technologie KIT filed Critical BASF SE
Priority to JP2014531136A priority Critical patent/JP2014526588A/ja
Priority to EP12730485.5A priority patent/EP2758439A1/fr
Priority to KR1020147007488A priority patent/KR20140078630A/ko
Priority to CN201280045749.7A priority patent/CN103842391A/zh
Publication of WO2013041257A1 publication Critical patent/WO2013041257A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Definitions

  • the present invention relates to a process for producing nanoparticles containing at least one polymer and / or copolymer by providing an aerosol containing droplets of at least one monomer and at least one photoinitiator in a gas stream, irradiating this aerosol stream with light so that the present monomers polymerize , and separating the nanoparticles formed from the gas stream, nanoparticles producible by this method and the use of these nanoparticles according to the invention in optical, electronic, chemical, biotechnological systems or for the application of active ingredient.
  • US 2007/0142589 A1 discloses a process for the preparation of polymeric microparticles.
  • a liquid containing corresponding monomeric compounds is atomized in order to obtain a droplet cloud of polymerization-initiated monomer droplets in a gas-filled reaction zone. Under the action of gravity, these liquid droplets fall through a reaction zone and begin to polymerize. The particles are then collected and removed from the reaction zone.
  • neutralized acrylic acid is sprayed in aqueous solution by means of a spray bottle in a reaction chamber at 50 to 80 ° C against a gas plate. After about one minute, corresponding microspheres can be detected on this gas plate.
  • Morita et al. disclose methods of making nanoparticles from organic materials, see, for example, Journal of Photopolymer Science and Technology, Volume 12, Number 1 (1999), 95-100, Journal of Photopolymer Science and Technology, Volume 12, Number 1 (1999) 101-106 , Journal of Photopolymer Science and Technology, Volume 13, Number 1 (2000), 159-162, Journal of Photochemistry and Photobiology, A: Chemistry, 150 (2002), 7-11, or Journal of Photochemistry and Photobiology, A: Chemistry, 103 (1997), 27-31.
  • the processes mentioned in these documents involve the preparation of nanoparticles from organic monomers.
  • US 2008/0187663 discloses a method for depositing polymeric materials on certain surfaces. For this purpose, a mixture containing polymerizable components is evaporated and deposited on the corresponding surfaces under reduced pressure.
  • the processes known from the prior art for the preparation of polymer particles have the disadvantage that the particle size can not be reliably predicted. Furthermore, the prior art methods are not accessible to particles which are characterized by a high uniformity, for example by a narrow particle size distribution or uniform particle shape or uniform particle composition. Also, the methods of the prior art are not suitable to produce nanoparticles with diameters smaller than 3 ⁇ . Furthermore, the prior art methods are not necessarily suitable for continuous driving.
  • nanoparticles comprising at least one polymer and / or copolymer by providing an aerosol containing droplets of at least one monomer and at least one photoinitiator in a gas stream, irradiating this aerosol stream with light so that the present monomers polymerize , and separating the formed nanoparticles from the gas stream.
  • the process according to the invention is preferably carried out continuously.
  • Nanoparticles containing at least one polymer and / or copolymer are accessible by the process according to the invention.
  • the term “ noparticles” particles with a diameter, ie the longest particle present in the distance, from 40 to 3000 nm, preferably 50 to 1000 nm, more preferably between 50 to 400 nm and 50 to 200 nm.
  • the particles produced contain at least one polymer and
  • the term "copolymer” is understood according to the invention to mean a polymer which is made up of at least two different monomers.
  • the nanoparticles produced according to the invention consist of at least one polymer and / or copolymer.
  • the nanoparticles prepared according to the invention additionally contain at least one nanoparticulate additive.
  • larger particles than the particles produced according to the invention can also be produced with the nebulizer or atomizer used according to the invention.
  • the direction of flow of the gas stream within the reactor is not crucial according to the invention.
  • the nanoparticles produced according to the invention may generally have any shape, preferably the nanoparticles are spherical, shell-shaped or hollow spheres or gel-like spheres.
  • the present invention therefore preferably relates to the method according to the invention, wherein the nanoparticles are spherical, shell-shaped or hollow spheres or gel-like spheres.
  • cup-shaped means that a particle is formed which has the above-mentioned diameter as outer diameter d a and has a concave indentation with a smaller inner diameter, this inner diameter d being the diameter of the largest sphere. which fits into the indentation without this ball protruding beyond the indentation, see also FIG. 3.
  • an aerosol comprising droplets of at least one monomer and at least one photoinitiator in a gas stream.
  • the gas stream may be an inert gas stream, for example selected from the group consisting of nitrogen (N 2 ), carbon dioxide (CO 2 ), argon (Ar), helium (He) and mixtures thereof, or air. If the polymerization according to the invention is initiated and carried out by free radicals, it is preferred to use an inert gas stream. If the polymerization according to the invention is initiated and carried out cationically, an air or inert gas stream is preferably used.
  • the present invention therefore preferably relates to the process according to the invention, wherein the gas stream is an inert gas stream, for example selected from the group consisting of nitrogen (N 2 ), carbon dioxide (C0 2 ), argon (Ar), helium (He) and mixtures thereof, and the polymer is formed by radical polymerization.
  • the gas stream is an inert gas stream, for example selected from the group consisting of nitrogen (N 2 ), carbon dioxide (C0 2 ), argon (Ar), helium (He) and mixtures thereof, and the polymer is formed by radical polymerization.
  • the present invention furthermore preferably relates to the process according to the invention, wherein the gas stream is an air stream or an inert gas stream, for example selected from the group consisting of nitrogen (N 2 ), carbon dioxide (CO 2 ), argon (Ar), helium (He) and mixtures thereof, and the polymer is formed by cationic polymerization.
  • the gas stream is an air stream or an inert gas stream, for example selected from the group consisting of nitrogen (N 2 ), carbon dioxide (CO 2 ), argon (Ar), helium (He) and mixtures thereof, and the polymer is formed by cationic polymerization.
  • all monomers can be used according to the invention, which are characterized by a high reactivity, ie. H. a high polymerization rate under the reaction conditions of the invention, distinguished.
  • the polymerization reaction takes place up to a residual monomer content in the particle of not more than 30%, preferably not more than 20%, more preferably not more than 10% within a time of less than 2 minutes, preferably less than 1.5 minutes, more preferably less than 1 minute is to be used, monomers are particularly preferably used in the process according to the invention, which have a correspondingly high rate of polymerization under the reaction conditions of the invention.
  • K p chain growth rate coefficient
  • the chain growth rate coefficient K p of the polymerization reaction is preferably greater than 500 mol / l / s, particularly preferably greater than 1 .000 mol / l / s, very particularly preferably greater than 2,000 mol / l / s, in particular greater than 5,000 mol / l / s , more preferably greater than 10,000 mol / l / s.
  • the present invention therefore preferably relates to the process according to the invention, wherein the chain growth rate coefficient K p of the polymerization reaction is greater than 500 mol / l / s, preferably greater than 1 .000 mol / l / s, more preferably greater than 2,000 mol / l / s, very particularly preferably greater than 5,000 mol / l / s, in particular greater than 10,000 mol / l / s, is.
  • reaction rate can also be described by the so-called Damköhler number Da, which forms the ratio of residence time in the reactor and reaction time:
  • reaction time results from the product of chain growth rate coefficient K p and average initial concentration of the mixture of monomer and crosslinker c 0 .
  • the residence time in the reactor ⁇ is calculated from the internal volume of the reactor divided by the aerosol volume flow.
  • the initial concentration is the weighted average of monomer and crosslinker concentration in the drop.
  • the Damköhler number Da of the polymerization reaction is preferably greater than 200,000, particularly preferably greater than 500,000, very particularly preferably greater than 1,000,000.
  • the present invention therefore preferably relates to the process according to the invention, wherein the Damköhler number Da of the polymerization reaction is greater than 200,000, preferably greater than 500,000, particularly preferably greater than 1,000,000.
  • the present invention therefore preferably relates to the process according to the invention, wherein the at least one monomer is selected from the group consisting of olefinically unsaturated, preferably ⁇ , ⁇ -unsaturated, monomers, epoxides, cyclic ethers, acetals and mixtures thereof.
  • ⁇ , ⁇ -unsaturated monomers are known in the art.
  • preferred ⁇ , ⁇ -unsaturated monomers are selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, styrene, styrene derivatives, vinylic monomers, acrylamides, methacrylamides and mixtures thereof.
  • acrylic esters and methacrylic esters are compounds of general formula (I)
  • R 1 is hydrogen (acrylic acid) or methyl (methacrylic acid) and
  • R 2 is a linear or branched, optionally substituted alkyl group having 1 to
  • the groups mentioned may optionally have further functional groups, for example alcohol, keto, ether groups or heteroatoms, for example N, O, P or S.
  • the said aryl and heteroaryl groups may optionally be attached via a saturated or unsaturated, optionally substituted carbon chain having 1 to 12 carbon atoms, preferably one or two carbon atoms, to the oxygen atom of the acid functionality.
  • Examples of optionally present heteroatoms are selected from the group consisting of N, O, P, S and mixtures thereof.
  • Styrene is known per se to the person skilled in the art and corresponds to the following formula (II)
  • styrene are, for example, corresponding compounds which are derived from styrene and carry further substituents on the aromatic ring and / or on the double bond, for example methyl.
  • a preferred styrene derivative is methyl styrene.
  • Epoxides are known per se to those skilled in the art and, for example, selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, styrene oxide and mixtures thereof.
  • the at least one monomer is preferably selected from the group consisting of acrylic acid, butyl acrylate (butyl acrylate), benzyl acrylate (benzyl acrylate), hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), alkyl 2-cyanoacrylates such as ethyl cyanoacrylate (E-CA), methacrylic acid, methyl methacrylate (methyl methacrylate, MMA) butyl methacrylate (butyl methacrylate), benzyl methacrylate (benzyl methacrylate), styrene, ⁇ - Methyl styrene, 4-vinylpyridine, vinyl chloride, vinyl alcohol, vinyl ethers, N-is
  • a cationic, photoinitiated polymerization preference is given to using vinyl ethers and / or isopropenylbenzene ( ⁇ -methylstyrene).
  • alkyl-2-cyanoacrylates preference is given to using alkyl-2-cyanoacrylates, acrylonitrile, styrene (derivatives), acrylates and / or epoxides.
  • an aerosol containing droplets of at least one monomer and at least one photoinitiator in a gas stream can generally be carried out by any method known to the person skilled in the art, or using the apparatuses generally known to the person skilled in the art.
  • the provision of the aerosol takes place in a nebulizer or atomizer, for example by Spraying of the monomer or of the monomer solution (containing monomers, photoinitiator, optionally additives such as nanoparticles, optionally crosslinker, optionally solvent, optionally cosolvent) by means of a two-fluid nozzle or with an electrospray or with an ultrasonic nebulizer.
  • the inventive method can be carried out at lower temperatures, so that a smaller proportion of the monomers evaporated. As a result, the droplet size more accurately determines the particle size.
  • the atomizer it is further possible, by choice of the atomizer, to set particularly narrow particle size distributions, e.g. by classifying the drops using a differential mobility analyzer (DMA).
  • DMA differential mobility analyzer
  • the gas stream generally has a flow rate of 0.1 to 100 cm / s, preferably 0.5 to 10 cm / s, more preferably 0.5 to 2 cm / s, at the location of the reactor where the polymerization reaction takes place ,
  • the aerosol provided by the invention contains droplets of at least one monomer and at least one photoinitiator in a gas stream.
  • the erfindungsge- Permitted method is preferably carried out so that a droplet concentration in the gas stream of preferably 10 6 to 10 10 droplets / cm 3, preferably 10 6 to 10 8 droplets / cm 3, most preferably 1 x 10 7 to 1 x 10 8 Droplets / cm 3 , for example 5 x 10 7 droplets / cm 3 , is present.
  • the droplet concentration can be determined, for example, using a Scanning Mobility Particle Sizer (SMPS) or a condensation particle counter.
  • SMPS Scanning Mobility Particle Sizer
  • N 2 nitrogen
  • This nitrogen may be from any source known to those skilled in the art, for example, from commercially available storage bottles, from the distillation of air etc.
  • the other inert gases mentioned may also originate from the sources known to the person skilled in the art.
  • the air used is preferably ambient or compressed air.
  • the pressure in the gas stream is according to the invention preferably at atmospheric pressure or slightly elevated atmospheric pressure.
  • "slightly elevated atmospheric pressure” means a pressure which is, for example, 1 to 500 mbar above atmospheric pressure. This preferably slightly elevated pressure serves, in particular, for the gas flow to overcome the resistance of a filter or a separating liquid.
  • the process according to the invention is preferably carried out at a temperature of from 10 to 80 ° C., preferably from 20 to 35 ° C., for example 30 ° C.
  • the advantage of the photopolymerization carried out according to the invention is that it can be carried out at low temperatures and thus fewer chain transfers take place.
  • the droplets contained in the aerosol provided according to the invention contain, in addition to the at least one monomer, at least one photoinitiator.
  • at least one photoinitiator it is possible to use all photoinitiators known to the person skilled in the art which comprise a free-radical or ionic, ie. H. cause cationic or anionic polymerization reaction of the at least one monomer used. Since the monomer mixture is irradiated with light for polymerization, it is preferred according to the invention to use photoinitiators which release a sufficiently large amount of (primary) radicals by irradiation with light.
  • light means UV light or visible light, ie electromagnetic radiation with a wavelength of 150 to 800 nm, preferably 180 to 500 nm, particularly preferably 200 to 400 nm, in particular 250 to 350 nm UV light is preferably used according to the invention.
  • inventively preferred photoinitiators for a radical polymerization are selected from the group consisting of 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (for example, available under the trade name Irgacure ® 907), 2, 2'-azobisisobutyronitrile (AIBN) and other non-symmetrical azo derivatives, benzoin, benzoin alkyl ethers, benzoin derivatives, acetophenones, benzil ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, O-acyl-a-oximinoketones (Bi) acylphosphine oxides, thioxanthone (derivatives) and Mixtures thereof.
  • 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one for example, available under the trade name Irgacure ® 907
  • AIBN 2, 2
  • photoinitiators for cationic photopolymerization which are preferred according to the invention are selected from the group consisting of substituted diaryliodonium salts, substituted triarylphosphonium salts and mixtures thereof.
  • inventively preferred photoinitiators for anionic photopolymerization are selected from the group consisting of transition metal complexes, N-alkoxypyridinium salts, N-Phenylacylpyridiniumsalzen and mixtures thereof.
  • a so-called living anionic polymerization in the pure polymer mixture, optionally comprising secondary functionalization by means of a termination reagent, for example by injection of a gaseous or vaporizable chemical compound into the aerosol space, preferably in the outlet section.
  • certain nanoparticles for example ZnO and / or TiO 2 in nanoparticulate form, can also be used as the photoinitiator. These are also preferably used according to the invention as an additive. Therefore, in a preferred embodiment of the process according to the invention, at least one nanoparticle, for example ZnO and / or TiO 2 in nanoparticulate form, is used simultaneously as a photoinitiator and as an additive.
  • the amount of photoinitiator in the droplets present in the aerosol provided according to the invention is, for example, 0.1 to 10% by weight, preferably 0.5 to 8% by weight, particularly preferably 0.8 to 6% by weight. , in each case based on the amount of the at least one monomer present.
  • the present invention relates to the method according to the invention, in which the droplets contain no solvent and nanoparticles are formed which have a spherical shape.
  • the droplets additionally contain at least one solvent.
  • the preferred embodiment according to the invention which contains at least one solvent in the droplets, it is preferred according to the invention to form nanoparticles which have a cup-shaped form.
  • the monomer solution containing at least one solvent it is also possible to produce hollow spheres or gel-like spheres.
  • the present invention therefore relates, in a preferred embodiment, to the method according to the invention, wherein at least one solvent is contained in the droplets and nanoparticles are formed which have a shell-shaped or hollow-spherical form.
  • Solvents which are preferred according to the invention are those in which the at least one monomer is soluble but the polymer formed is insoluble.
  • preferred solvents according to the invention are polar organic solvents such as alcohols, ketones, esters of carboxylic acids or mixtures thereof or polar aprotic organic solvents such as acetonitrile.
  • Other possible solvents are hexane, (methyl) cyclohexane, cyclic ethers such as THF, dioxane or ionic liquids. Mixtures of the solvents mentioned are also possible.
  • Suitable alcohols are, for example, selected from the group consisting of methanol, ethanol, propanols, such as n-propanol, isopropanol, butanols, such as n-butanol, isobutanol, tert-butanol, pentanols and mixtures thereof.
  • Suitable ketones according to the invention are for example selected from the group consisting of acetone, methyl ethyl ketone and mixtures thereof.
  • Suitable esters of carboxylic acids according to the invention are, for example, selected from the group consisting of ethyl acetate, methyl acetate and mixtures thereof.
  • the at least one monomer can also function as solvent.
  • the process parameters are set so that not all monomer is converted. Not everything is implemented, for example, up to a residual monomer content in the particle of not more than 30%, preferably not more than 20%, particularly preferably not more than 10%, and the remainder evaporates, so that the residual monomer content in the finished particles can nevertheless be very low.
  • Ethanol or 1-propanol (n-propanol) is particularly preferably used as the solvent according to the invention.
  • the at least one solvent according to the invention for example, in an amount of 10 to 80 vol .-%, preferably 30 to 70 vol .-%, particularly preferably 40 to 60 vol .-%, each based on the amount of at least one monomer used.
  • the droplets additionally contain at least one crosslinker.
  • the present invention therefore preferably relates to the process according to the invention, wherein the droplets additionally contain at least one crosslinker.
  • Crosslinkers which can be used according to the invention are known per se to the person skilled in the art.
  • the crosslinkers bring about in the polymerization reaction of the monomers provided a crosslinking and thus an increase in the molecular weight of the polymers obtained.
  • suitable crosslinkers are selected from the group consisting of 1,6-hexanediol diacrylate (HDDA), diethylene glycol dimethacrylate (EGDMA), allyl methacrylate (AMA), trifunctional acrylates such as trimethylolpropane trimethacrylate (PMPTMA), and mixtures thereof.
  • the at least one crosslinker is used according to the invention, for example, in an amount of from 2 to 80% by volume, preferably from 2 to 20% by volume, particularly preferably from 3 to 15% by volume, based in each case on the amount of the at least one monomer.
  • At least one cosolvent can additionally be added to the droplets.
  • this co-solvent serves to positively influence the particle structure by changing the physical, chemical or mechanical properties during the polymerization, for example solution properties of monomers and polymers, surface tension, vapor pressure, drop stability or viscosity.
  • the cosolvent is selected, for example, from the group consisting of glycerol, glycol, polyethylene glycol, EO / PO copolymers, silicone oils and mixtures thereof.
  • the present invention therefore preferably relates to the process according to the invention, wherein the droplets additionally comprise at least one cosolvent selected from the group consisting of glycerol, glycol, polyethylene glycol, EO / PO copolymers, silicone oils and mixtures thereof.
  • the droplets additionally contain at least one further additive.
  • the present invention therefore preferably relates to the process according to the invention, wherein the droplets additionally contain at least one further additive.
  • additives can be used which appear to be suitable for the person skilled in the art.
  • Preferred examples of corresponding additives are inorganic materials and / or active substances, for example pharmaceutical, biological, insecticidal, pesticidal active substances. It is essential for the optionally present additives that they do not absorb all the radiation which is made available when irradiating the gas stream with light, preferably UV light.
  • the additives mentioned are preferably in nanoparticulate or dissolved form.
  • the optionally additionally present additives are metals or metal and / or semi-metal oxides, for example selected from the group consisting of ZnO, Ti0 2 , Fe oxides such as FeO, Fe 2 0 3 , Fe 3 0 4 , Si0 2 and Mixtures of it.
  • the at least one additive in particular the metal and / or semimetal oxide, is in nanoparticulate form, ie. H. with a diameter of 1 to 400 nm, preferably 5 to 100 nm, in particular 10 to 50 nm, before.
  • the nanoparticles may be of any shape, e.g. B. spherical, cube-shaped, rod-shaped.
  • the at least one additive according to the invention for example, in an amount of 0.1 to 40 wt .-%, preferably 0.5 to 25 wt .-%, particularly preferably 0.6 to 22 wt .-%, each based on the amount of at least one monomer used.
  • hybrid nanoparticles containing at least one polymer and / or copolymer and at least one additive are obtained. These are preferably in spherical form.
  • the hybrid nanoparticles according to the invention may also preferably be shell-shaped.
  • the droplet diameter is preferably set by the choice of operating conditions of the atomizer, for example by the pre-atomizer pressure, gas / liquid ratio, etc.
  • the voltage can be varied, for an ultrasonic atomizer the energy input .
  • a specific size fraction can be selected by a differential mobility analyzer (DMA)
  • DMA differential mobility analyzer
  • the amount of at least one monomer and at least one photoinitiator, which are introduced into the gas stream, according to the invention is such that a corresponding number of particles per volume is obtained.
  • the size of the liquid droplets formed in the aerosol and thus the size of the nanoparticles obtained after the polymerization can be calculated.
  • Preferred diameters of the droplets present in the aerosol are, for example, 40 to 3000 nm, preferably 50 to 1000 nm, particularly preferably 50 to 400 nm or 50 to 200 nm.
  • the size of the nanoparticles to be produced can be adjusted in a targeted manner.
  • the size of the nanoparticles produced according to the invention is therefore for example 40 to 3000 nm, preferably 50 to 1000 nm, more preferably 50 to 400 nm or 50 to 200 nm.
  • light preferably UV Light
  • the irradiation of the gas stream with light according to the invention can generally be carried out in any device known to the person skilled in the art. UV light is preferably used according to the invention.
  • the use of an excimer radiator is advantageous since it can be dimmed by pulsed operation, for example to 10 to 100%. As a result, an optimization of the polymerization process is relatively easy.
  • the reactor inner wall is flushed with an inert gas, for example with N 2 , Ar, He, CO 2 or mixtures thereof. This serves, for example, to suppress wall losses through polymer film formation.
  • an inert gas for example with N 2 , Ar, He, CO 2 or mixtures thereof.
  • the molecular weight of the at least one polymer and / or copolymer produced according to the invention is generally from 1 000 to 1 000 000 g / mol, preferably from 10 000 to 100 000 g / mol.
  • the nanoparticles formed are separated off.
  • the separation can be carried out in principle according to all methods known in the art.
  • the separation of the nanoparticles formed takes place by deposition on the surface of a filter or by introduction into a liquid medium.
  • the present invention therefore preferably relates to the process according to the invention, wherein the separation of the nanoparticles formed takes place by deposition on a surface of a filter or by introduction into a liquid medium.
  • Suitable filters are known per se to those skilled in the art, for example polyamide, polycarbonate filters, PTFE filters, for example with pore sizes of 50 nm, electrostatic precipitators.
  • the deposition in a liquid can be done for example with a wash bottle or a wet electrostatic precipitator.
  • the optionally used liquid medium may be selected from the group consisting of water, ethanol, organic solvents, for example the abovementioned, non-polar solvents of all kinds, for example alkanes, cycloalkanes and mixtures thereof.
  • a suspension of the particles in the liquid medium Erfindungsge- measure this suspension can be further processed, for example by separating the particles from the suspension.
  • this suspension is the desired process product according to the invention and can be introduced directly into the corresponding application.
  • the present invention also relates to nanoparticles producible by the method according to the invention. These are characterized by a particularly uniform shape, either shell-shaped or spherical, hollow sphere or gel-like spheres, and / or by a particularly narrow particle size distribution.
  • the nanoparticles prepared according to the invention are particularly suitable for applications in optical, electronic, chemical, biotechnological systems or for drug application.
  • the present invention therefore preferably relates to the use of the nanoparticles according to the invention in optical, electronic, chemical, biotechnological systems or for the application of active ingredient.
  • the present invention therefore preferably relates to the use according to the invention, wherein the nanoparticles are used as photosensitizers and / or photoinitiators.
  • FIG. 1 shows a scanning electron micrograph of crosslinked PMMA polymer particles which have been produced by the process according to the invention.
  • FIG. 2 shows photographs of nanostructured polymer particles. On the left are nanoshells (scanning electron micrograph), on the right are hybrid nanoparticles consisting of ZnO nanoparticles and a polymer (transmission electron micrograph).
  • FIG. 3 shows a schematic illustration of a shell-shaped particle.
  • d a is the outer diameter and d
  • the inner diameter, d results from the diameter of the largest ball, which finds place in the recess, without this ball protrudes beyond the recess.
  • FIG. 4 shows a characteristic particle size distribution according to the invention. The x-axis shows the diameter of the particles in nm, the y-axis describes the number of particles per cm 3 .
  • FIG. 5 shows a scanning electron micrograph of nanoshells with benzyl methacrylate as monomer according to Example 23.
  • FIG. 6 shows a scanning electron micrograph of hybrid nanoshells with methyl methacrylate as monomer and ZnO as nanoparticles according to Example 24.
  • FIG. 7 shows a transmission electron micrograph of hybrid nanoshells with methyl methacrylate as monomer and ZnO as nanoparticles according to Example 24.
  • FIG. 8 shows a scanning electron micrograph of copolymer particles formed with butyl acrylate (BA) and methyl methacrylate (MMA) as monomers according to Example 29.
  • the built-up laboratory facilities consist essentially of a commercially available atomizer and a self-constructed photoreactor.
  • a solution is first prepared. This solution includes one or more monomers, the photoinitiator and optionally a crosslinker.
  • the prepared solution is added to the atomizer with two-fluid nozzle and atomized with the aid of nitrogen (N 2 ).
  • the nitrogen-borne droplet aerosol from nanoscale monomer droplets is passed through the flow-through photoreactor, where the photo-initiated polymerization of the monomer droplets to nanoscale polymer particles or copolymer particles takes place.
  • the gas-borne particles are then either deposited on a filter or transferred to the liquid phase.
  • the following emitters are used: Excimer XeCI emitter (10 mW / cm 2 on the emitter surface)
  • UV fluorescence tube (8 mW / cm 2 on the radiator surface)
  • the starting solution Before the atomization, the starting solution can be mixed with a solvent and / or cosolvent to obtain To form nanoshells (nanoshells) in the photoreactor ( Figure 2, left).
  • Hybrid nanoparticles can be prepared by suspending inorganic particles in the starting solution and atomising them with the solution ( Figure 2, right). The following examples give the composition of the solutions used.
  • MMA methyl methacrylate
  • the crosslinker is 1,6-hexanediol diacrylate (HD DA, 5% by volume with respect to MMA) and the photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1% by weight in MMA).
  • MMA methyl methacrylate
  • HDDA 1,6-hexanediol diacrylate
  • Irgacure 907 5 wt .-% in MMA
  • glycerol 26.18 wt .-% in MMA
  • Example 3 For the preparation of the nanoscale hybrid particles, a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 1, 74% by weight in MMA) and methyl methacrylate (MMA) is used as the monomer.
  • the crosslinker used is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to MMA) and the photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1 % By weight in MMA). It is generated in a proportion of> 98% hybrid particles.
  • HDDA 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • Example 4 For the preparation of the other homopolymers of polymethyl methacrylate, a solution with methyl methacrylate (MMA) is used as a monomer.
  • the crosslinker is 1,6-hexanediol diacrylate (HD DA, 10% by volume with respect to MMA) and the photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1% by weight in MMA). Nanoparticles in the size range of 60 to 350 nm are obtained (more than 75% of the particles in this range).
  • MMA methyl methacrylate
  • HD DA 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • Example 6 For the preparation of the homopolymers of polybutyl acrylate, a solution with butyl acrylate (BA) is used as the monomer.
  • the crosslinker used is 1,6-hexanediol diacrylate (HD DA, 10% by volume with respect to MMA) and the photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1% by weight in MMA).
  • HD DA 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • a solution with butyl acrylate (BA) is used as monomer.
  • No crosslinker is used and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1% by weight in MMA) is used as the photoinitiator.
  • Nanoparticles in the size range of 60 to 350 nm are obtained (more than 75% of the particles in this range).
  • a solution with benzyl methacrylate (BzMA) is used as a monomer.
  • the crosslinker is 1,6-hexanediol diacrylate (HD DA, 10% by volume with respect to MMA) and the photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1 wt .-% in MMA) used.
  • Nanoparticles in the size range of 60 to 300 nm are obtained (more than 75% of the particles in this range).
  • a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 21, 01% by weight in MMA) and methyl methacrylate (MMA) is used as the monomer.
  • the crosslinker used is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to MMA) and the photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1 % By weight in MMA).
  • a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 0.64% by weight in BzMA) and benzyl methacrylate (BzMA) is used as the monomer.
  • the crosslinker used is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to BzMA) and, as photoinitiator, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1 % By weight in BzMA). It is generated in a proportion of> 98% hybrid particles.
  • a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 0.74% by weight in BA) and butyl acrylate (BA) is used as the monomer.
  • the crosslinker is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to BA) and, as photoinitiator, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1 % By weight in BA).
  • nanoscale hybrid particles For the preparation of the nanoscale hybrid particles, a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 0.74% by weight in BA) and butyl acrylate (BA) is used as the monomer. There is no crosslinker used and as a photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 1 % By weight in BA). Nanoparticles in the size range of 70 to 400 nm are obtained (more than 75% of the particles in this range). It is generated to a share of> 95% hybrid particles.
  • a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 0.74% by weight in BA) and butyl acrylate (BA) is used as the monomer.
  • the crosslinker used is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to BA).
  • the zinc oxide particles serve as photoinitiator. It is generated to a share of> 95% hybrid particles.
  • a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 0.74% by weight in BA) and butyl acrylate (BA) is used as the monomer. There is no crosslinker used.
  • the zinc oxide particles serve as photoinitiators. It is generated in a proportion of> 98% hybrid particles.
  • MMA methyl methacrylate
  • 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1 - ⁇ is used. This will not produce any particles.
  • Example 16 For the preparation of the nanoshells, a solution of methyl methacrylate (MMA) as monomer and 1-propanol (45.45% by volume in MMA) as solvent is prepared. Therein are 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to MMA) as crosslinking agent, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 5% by wt .- % in MMA) as photoinitiator and glycerol (26.18 wt% in MMA). The proportion of particles in shell form is greater than 98%.
  • HDDA 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • Irgacure 907 5% by wt .- % in MMA
  • MMA methyl methacrylate
  • HDDA 1,6-hexanediol diacrylate
  • Irgacure 907 5% by wt .-% in MMA
  • glycerol 26.18 wt .-% in MMA
  • MMA methyl methacrylate
  • 1-propanol 45.45% by volume in MMA
  • solvent 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • glycerol 26.18% by weight in MMA
  • styrene For the preparation of homopolymers of polystyrene, a solution with styrene as a monomer is used.
  • the crosslinker is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to styrene) and, as photoinitiator, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 5 % By weight in styrene).
  • HDDA 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • a solution with styrene and methyl methacrylate (MMA) is used as the monomer.
  • the volume ratio of MMA to styrene is 3.
  • the crosslinker used is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to MMA + styrene) and, as photoinitiator, 2-methyl-1 [4- (methylthio) phenyl] -2 -morpholinopropan-1-one (Irgacure 907, 5 wt .-% in MMA + styrene) used.
  • Example 21 Nanoshells with Butyl Acrylate as Monomer
  • BA butyl acrylate
  • ethanol 45.45% by volume in BA
  • solvent 1,6-hexanediol diacrylate
  • Irgacure 907 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one
  • % in BA) photoinitiator and glycerol (27.07% by weight in BA).
  • Example 21b Nanoshells with butyl acrylate as monomer
  • a solution of butyl acrylate (BA) as a monomer and ethanol (45.45% by volume in BA) as solvent is prepared.
  • No crosslinker is used and the solution is 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-o (Irgacure 907, 5 wt .-% in BA) as a photoinitiator and glycerol (15, 65% by weight in BA).
  • Example 22 Hybrid particles with MMA as monomer and without Irgacure 907
  • a suspension of zinc oxide particles in ethanol (40% by weight of ZnO in ethanol / 6.62% by weight in MMA) and methyl methacrylate (MMA) is used as the monomer.
  • the crosslinker used is 1,6-hexanediol diacrylate (HDDA, 10% by volume with respect to MMA).
  • the ZnO particles serve as photoinitiator.
  • benzyl methacrylate (BzMA) as a monomer and ethanol (45.45 vol% in BzMA) as a solvent is prepared.
  • BzMA benzyl methacrylate
  • HDDA 1,6-hexanediol diacrylate
  • 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, 5 wt % in BzMA) as a photoinitiator and glycerol (24.27% by weight in BzMA).
  • Example 24 Hybrid nanoshells with methyl methacrylate as monomer
  • the monomer used is methyl methacrylate (MMA).
  • the crosslinker is 1,6-hexanediol diacrylate (HD DA, 10% by volume with respect to MMA) and the photoinitiator is 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 , 5 wt .-% in MMA) dissolved in the monomer.
  • This solution is dissolved in ethanol (45.45% by volume of ethanol in MMA).
  • Glycerol is also dissolved in this solution (26.18 wt% in MMA).
  • the resulting solution is mixed with a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 0.50% by weight in MMA) to form a monomer suspension.
  • Example 25 Hybrid nanoshells with methyl methacrylate as monomer
  • the monomer used is methyl methacrylate (MMA).
  • the crosslinker is 1,6-hexanediol diacrylate (HD DA, 10% by volume with respect to MMA) and the photoinitiator is 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 , 5 wt .-% in MMA) dissolved in the monomer.
  • This solution is dissolved in ethanol (45.45% by volume of ethanol in MMA).
  • Glycerol is also dissolved in this solution (26.18 wt% in MMA).
  • the resulting solution is mixed with a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 1, 50% by weight in MMA) to form a monomer suspension.
  • Example 26 Hybrid nanoshells with methyl methacrylate as monomer
  • the monomer used is methyl methacrylate (MMA).
  • the crosslinker is 1,6-hexanediol diacrylate (HD DA, 10% by volume with respect to MMA) and the photoinitiator is 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 , 5 wt .-% in MMA) dissolved in the monomer.
  • This solution is dissolved in ethanol (45.45% by volume of ethanol in MMA).
  • Glycerol is also dissolved in this solution (26.18 wt% in MMA).
  • the resulting solution is mixed with a suspension of zinc oxide particles in ethanol (40% by weight ZnO in ethanol / 3.00% by weight in MMA) to form a monomer suspension.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • MMA methyl methacrylate
  • the volume ratio of MMA to BA is 9/1.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • MMA methyl methacrylate
  • the volume ratio of MMA to BA is 7/3.
  • Example 31 Copolymer For the preparation of the copolymers of butyl acrylate (BA) and methyl methacrylate (MMA), a solution with butyl acrylate and methyl methacrylate (MMA) as monomer is used. The volume ratio of MMA to BA is 3/7. There is no crosslinker used and as a photoinitiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1 - ⁇ (Irgacure 907, 1 wt .-% in MMA + BA).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production de nanoparticules contenant au moins un polymère et/ou un copolymère par la préparation d'un aérosol contenant des gouttelettes à partir d'au moins un monomère et d'au moins un photo-amorceur dans un courant gazeux, l'exposition de ce courant d'aérosol à la lumière, de telle sorte que les monomères présents polymérisent, et la séparation des nanoparticules formées du courant gazeux, des nanoparticules pouvant être produites grâce audit procédé. La présente invention concerne également l'utilisation de ces nanoparticules selon la présente invention dans des systèmes optiques, électroniques, chimiques, biotechnologiques ou pour l'application de principes actifs.
PCT/EP2012/062099 2011-09-23 2012-06-22 Photopolymérisation d'aérosol Ceased WO2013041257A1 (fr)

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JP2014531136A JP2014526588A (ja) 2011-09-23 2012-06-22 エアロゾルの光重合
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KR1020147007488A KR20140078630A (ko) 2011-09-23 2012-06-22 에어로졸 광중합
CN201280045749.7A CN103842391A (zh) 2011-09-23 2012-06-22 气溶胶光聚合

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US20070142589A1 (en) 2004-02-24 2007-06-21 Rogers Martin E Process and systems for the efficient production of polymeric microspheres
WO2007104750A2 (fr) * 2006-03-13 2007-09-20 Basf Se Procédé de fabrication de nanoparticules polymères
CN101186706A (zh) * 2007-11-15 2008-05-28 天津大学 一种peg系凝胶纳米颗粒的制备方法
US20080187663A1 (en) 2007-02-06 2008-08-07 Sion Power Corporation Co-flash evaporation of polymerizable monomers and non-polymerizable carrier solvent/salt mixtures/solutions
DE102009006943A1 (de) * 2009-01-30 2010-08-05 Philipps-Universität Marburg Verfahren zur Herstellung photovernetzbarer Nanopartikel im kontinuierlichen Reaktor
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WO2007104750A2 (fr) * 2006-03-13 2007-09-20 Basf Se Procédé de fabrication de nanoparticules polymères
US20080187663A1 (en) 2007-02-06 2008-08-07 Sion Power Corporation Co-flash evaporation of polymerizable monomers and non-polymerizable carrier solvent/salt mixtures/solutions
CN101186706A (zh) * 2007-11-15 2008-05-28 天津大学 一种peg系凝胶纳米颗粒的制备方法
DE102009006943A1 (de) * 2009-01-30 2010-08-05 Philipps-Universität Marburg Verfahren zur Herstellung photovernetzbarer Nanopartikel im kontinuierlichen Reaktor
WO2010121387A1 (fr) * 2009-04-20 2010-10-28 ETH Zürich Nanoparticules polymères

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