EP2892932A1 - Précipitation de nanoparticules dans des monomères pour la production de particules hybrides - Google Patents

Précipitation de nanoparticules dans des monomères pour la production de particules hybrides

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Publication number
EP2892932A1
EP2892932A1 EP13765300.2A EP13765300A EP2892932A1 EP 2892932 A1 EP2892932 A1 EP 2892932A1 EP 13765300 A EP13765300 A EP 13765300A EP 2892932 A1 EP2892932 A1 EP 2892932A1
Authority
EP
European Patent Office
Prior art keywords
compound
inorganic material
precursor compound
polymeric
organic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13765300.2A
Other languages
German (de)
English (en)
Inventor
Wolfgang Gerlinger
Bernd Sachweh
Lena HECHT
Marion Winkelmann
Heike Schuchmann
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
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 EP13765300.2A priority Critical patent/EP2892932A1/fr
Publication of EP2892932A1 publication Critical patent/EP2892932A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3072—Iron sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the present invention relates to a process for the preparation of hybrid nanoparticles comprising at least one inorganic material and at least one polymeric organic material comprising at least the steps of (A) providing an emulsion comprising a disperse phase ( I) containing at least one precursor compound of the at least one polymeric, organic material, and at least one compound which effects the precipitation of the at least one inorganic material, a continuous, aqueous phase (II), and optionally at least one compound containing the Polymerizing the at least one precursor compound, which is present in the disperse phase (I), in the continuous, aqueous phase (II) or in both phases (I) and (II), (B) adding at least one precursor compound of the at least one inorganic material to the emul (C) optionally adding at least one compound which effects the polymerization of the at least one precursor compound of the at least one polymeric organic material, if any not in step (A), and (D) polymerizing the at least one precursor compound of the at least one poly
  • the present invention relates to nanoparticles producible by the method according to the invention and to the use of a nanoparticle according to the invention in optical, electronic, chemical, agrochemical, medical, pharmaceutical and / or biotechnological systems or for the administration of at least one active substance.
  • Methods for producing hybrid nanoparticles containing inorganic material and organic polymeric material are already known in the art.
  • a mini-emulsion of water in oil is prepared, wherein in the water droplets corresponding metal oxide precursor compounds, such as iron (III) chloride, is present.
  • metal oxide precursor compounds such as iron (III) chloride
  • To the continuous oil phase is added a compound, for example an amine, which through the oil phase in the dispersed water droplets, so that in these the present iron (III) chloride can be converted by precipitation into solid iron oxide.
  • the object of the present invention was therefore to provide a process for the preparation of hybrid nanoparticles containing at least one inorganic material and at least one polymeric, organic material in as few reaction steps as possible, wherein it should be avoided in particular that after the preparation of the inorganic materials these must be converted into a further emulsion for the preparation of the polymeric fraction.
  • This object is achieved according to the invention by a process for producing hybrid nanoparticles comprising at least one inorganic material and at least one polymeric, organic material comprising at least the steps:
  • step (B) adding at least one precursor compound of the at least one inorganic material to the emulsion of step (A) such that in the disperse phase the at least one inorganic material forms by precipitation,
  • step (C) optionally adding at least one compound which effects the polymerization of the at least one precursor compound of the at least one polymeric organic material, if not in step (A), and
  • the object according to the invention is achieved by nanoparticles, which can be prepared by the process according to the invention, and by the use of these nanoparticles in an optimal manner. see, electronic, chemical, agrochemical, medical engineering, pharmaceutical and / or biotechnological systems or for the administration of at least one active substance.
  • Step (A) of the process of the invention comprises providing an emulsion comprising a disperse phase (I) comprising at least one precursor compound of the at least one polymeric organic material, and at least one compound which effects the precipitation of the at least one inorganic material, a continuous one , aqueous phase (II), and optionally at least one compound which effects the polymerization of the at least one precursor compound, wherein these in the disperse phase (I), in the continuous, aqueous phase (II) or in both phases (I) and ( II) is present.
  • a disperse phase (I) comprising at least one precursor compound of the at least one polymeric organic material, and at least one compound which effects the precipitation of the at least one inorganic material, a continuous one , aqueous phase (II), and optionally at least one compound which effects the polymerization of the at least one precursor compound
  • the disperse phase (I) contains at least one precursor compound of the at least one polymeric, organic material.
  • at least one polymeric organic material is preferably a polymer and / or copolymer. Therefore, it is further preferred according to the invention that the at least one precursor compound of the at least one polymeric, organic material contained in the disperse phase (I) is a polymerisable or copolymerizable monomer.
  • the present invention therefore preferably relates to the process according to the invention, wherein the at least one precursor compound of the at least one polymeric, organic material is a polymerizable or copolymerizable monomer.
  • the at least one precursor compound of the at least one polymeric, organic material is at least one olefinically unsaturated, preferably ⁇ , ⁇ -unsaturated, monomer.
  • the present invention therefore further preferably relates to the process according to the invention, wherein the at least one precursor compound of the at least one polymeric organic material, in particular the at least one monomer, is selected from the group consisting of olefinically unsaturated, preferably ⁇ , ⁇ -unsaturated monomers and mixtures thereof ,
  • Monomers in particular ⁇ , ⁇ -unsaturated monomers, which are preferably used in the process according to the present invention are selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, styrene, styrene derivatives, vinylic monomers, for example vinyl acetate, isocyanates, acrylamides, methacrylamides and mixtures thereof.
  • Acrylic acid, methacrylic acid, acrylic esters and methacrylic esters, which are preferably used according to the invention, are compounds of the general formula (I)
  • R 1 is hydrogen (acrylic acid) or methyl (methacrylic acid)
  • R 2 represents a linear or branched, optionally substituted alkyl group having 1 to 12 carbon atoms, a linear or branched, optionally substituted alkenyl group having 2 to 12 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms or an optionally substituted heteroaryl group having 4 to 18 carbon atoms ,
  • alkyl, alkenyl, aryl or heteroaryl groups may optionally contain further functional groups, for example alcohol, keto or ether groups, or heteroatoms, for example N, O, P or S.
  • aryl and heteroaryl groups may optionally be bonded to the oxygen atom of the carboxylic acid functionality by means of a saturated or unsaturated, optionally substituted carbon chain having 1 to 12 carbon atoms, preferably 1 or 2 carbon atoms.
  • Styrene is known per se to a 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, for example methyl, on the aromatic ring and / or on the double bond.
  • a preferred styrene derivative is a-methyl-styrene.
  • isocyanates can also be used according to the invention.
  • Isocyanates used according to the invention are preferably polyisocyanates, ie they contain at least two isocyanate groups. These polyisocyanates preferably react with alcohols, amines or hydroxyamines present in the mixture, preferably with diols, diamines and / or hydroxyamines, to give corresponding polyurethanes or polyureas.
  • Corresponding isocyanates, alcohols, amines and / or hydroxyamines are known per se to the person skilled in the art.
  • Suitable isocyanates are, for example, toluene-2,4-diisocyanate (TDI), diphenylmethane diisocyanate or methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HMDI), polymeric diphenylmethane diisocyanate (PMDI), isophorone diisocyanate (IPDI), 4,4'- Diisocyanatodicyclohexylmethane or mixtures thereof.
  • Suitable diols are, for example, aliphatic or aromatic diols, polyether polyols, polyester polyols or mixtures thereof.
  • the at least one monomer is selected from the group consisting of acrylic acid, butyl acrylate, benzyl acrylate, hydroxyethyl methacrylate (HEMA), methacrylic acid 2-hydroxypropyl ester (HPMA), 2-cyanoacrylic acid alkyl ester, such as acrylic acid cyanoethyl ester (ECA), methacrylic acid, methyl methacrylate (MMA), butyl methacrylate, benzyl methacrylate, styrene, ⁇ -methylstyrene, 4-vinylpyridine, vinyl chloride, vinyl alcohol, vinyl acetate, vinyl ether, N-isopropylacrylamide (NIPAM), acrylamide, methac - Rylamid, isocyanates and mixtures thereof.
  • HEMA hydroxyethyl methacrylate
  • HPMA methacrylic acid 2-hydroxypropyl ester
  • 2-cyanoacrylic acid alkyl ester such as acrylic acid cyanoethyl
  • the at least one polymeric organic material is selected from the group consisting of polystyrene, poly ( ⁇ -methyl-styrene), poly (4-vinylpyridine), poly (vinyl chloride), poly (vinyl alcohol), poly (vinyl acetate), poly (vinyl ethers), polyacrylamides, polyurethanes, polyureas, poly (meth) acrylic acid, poly (meth) acrylic esters, copolymers containing two or more of the monomers contained in the aforementioned polymers and mixtures thereof.
  • the corresponding monomers mentioned above are preferably used according to the invention.
  • the at least one precursor compound of the at least one polymeric, organic material is present, preferably in an amount of from 70 to 98% by weight, preferably from 80 to 96% by weight, particularly preferably from 90 to 95% by weight , in each case based on the entire disperse phase.
  • the emulsion provided in step (A) of the process of the invention further comprises, in a preferred embodiment, at least one compound which effects the polymerization of the at least one precursor compound of the at least one polymeric organic material.
  • this at least one compound which effects the polymerization of the at least one precursor compound of the at least one polymeric organic material can also be added in step (C), ie after the inorganic material has been formed by precipitation.
  • the present invention therefore preferably relates to the process according to the invention, wherein the at least one compound which effects the polymerization of the at least one precursor compound is added in step (A). In this preferred embodiment, step (C) may be omitted.
  • the polymerization in step (D) can preferably be initiated thermally and / or photolytically.
  • the present invention therefore preferably relates to the process according to the invention, wherein the polymerization in step (D) is initiated thermally and / or photolytically.
  • the thermally and / or photolytically initiated polymerization can be free-radical, anionic or cationic.
  • step (C) the disperse or continuous phase of the emulsion according to step (A) of the process according to the invention, a corresponding compound causing the polymerization is added.
  • the polymerization is initiated thermally and takes place radically.
  • At least one compound which effects the polymerization is preferably selected from radical-forming compounds which form radicals by thermal treatment, particularly preferably selected from the group consisting of 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2 'azobis (2-methylpropionate), dimethyl 2,2'-azobisisobutyrate, 2,2'-azoisobutyronitrile (AIBN), dibenzoyl peroxide, water-soluble initiators, for example, potassium peroxodisulfate, and mixtures thereof. Water-soluble initiators are preferably used according to the invention if the addition takes place only in step (C).
  • photoinitiators compounds which bring about polymerization, which photolytically initiate the polymerization, so-called photoinitiators.
  • photoinitiators These are known to the person skilled in the art and can initiate a free-radical or ionic, for example cationic or anionic, polymerization reaction of the at least one monomer present. Since in the use of photoinitiators they must be irradiated with light to initiate a polymerization, photoinitiators are used according to the invention, which generate a sufficiently large amount of (primary) free radicals by irradiation with light.
  • the term "light” refers to UV light or visible light, for example electromagnetic radiation having a wavelength of 150 to 800 nm, preferably 180 to 500 nm, more preferably 200 to 400 nm, especially It preferably 250 to 350 nm. It is preferred that according to the invention photoinitiators are used which form corresponding radicals by irradiation with UV light.
  • Photoinitiators according to the invention is preferably used for a radical polymerization are selected from the group consisting of 2-methyl-1 - [4- (methylthio) phenyl] -2-morpholino-propan-1 - ⁇ (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, o
  • Aminoalkylphenone acyl- ⁇ -maximinoketones (bi) azylphosphine oxides, dioxantones and derivative, and mixtures thereof.
  • Photoinitiators which are preferred according to the invention in order to produce a cationically initiated polymerization are, for example, selected from the group consisting of substituted diaryliodonium salt, substituted triarylphosphonium salts and mixtures thereof.
  • photoinitiators which are preferably used according to the invention in order to initiate anionic polymerization are preferably selected from the group consisting of transition metal complexes, n-alkoxypyridinium salts, n-phenylacylpyridinium salts and mixtures thereof.
  • a so-called "living polymerization” can also be carried out, which is carried out either in the pure polymer mixture, optionally comprising a secondary functionalization by a chain-terminating reagent
  • the amount of at least one compound containing a polymerization, in particular a thermally initiated radical polymerization in the disperse phase (I) starts, according to the invention, for example, 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-% and more preferably 0.8 to 6 wt .-%, in In any case, based on the entire disperse phase I.
  • at least one compound which causes the precipitation of the at least one inorganic material is present.
  • the at least one compound which effects the precipitation of the at least one inorganic material is, according to the invention, selected so that it reacts with the at least one precursor compound of the inorganic material in the disperse phase to form the inorganic material.
  • a basic compound is preferably used as at least one compound which effects the precipitation of the at least one inorganic material.
  • the at least one compound which effects the precipitation of the at least one inorganic material according to the invention is selected from the group consisting of alkylamine, for example triethylamine, octylamine and mixtures thereof.
  • the at least one compound which effects the precipitation of the at least one inorganic material is, for example, according to the invention in an amount of 0.001 to 2% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5 Wt .-%, each based on the total emulsion before.
  • the emulsion provided in step (A) of the process according to the invention comprises the at least one disperse phase (I) in addition to the continuous, aqueous phase (II), for example in an amount of from 2 to 30% by weight, preferably from 6 to 20% by weight. %, more preferably 8 to 12 wt .-%.
  • the emulsion provided in step (A) of the process according to the invention comprises a continuous, aqueous phase (II), preferably in an amount of 70 to 98% by weight, preferably 80 to 94% by weight, particularly preferably 88 to 92% by weight .-%.
  • the amounts for the disperse phase (I) and the continuous, aqueous phase (II) add up in each case to 100 wt .-%.
  • the continuous, aqueous phase (II) present according to the invention contains water as the main constituent, preferably demineralized water.
  • the continuous, aqueous phase (II) additionally contains at least one emulsifier, for example selected from the group consisting of sorbates, for example polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80 and / or polysorbate 85, for example available under the trade name Tween, sodium dodecylsulfate (SDS), alkylpolyethylene glycol ethers, for example Lutensol AT 50 or Lutensol AT 80, decaglyceryl monostearate, for example SY Glyster ML-750), fatty alcohol ethoxylates, for example Emulgin B1, Emulan AF, Emulan AT 9, sodium nonylphenyl polyglycol ether sulfates , for example Emulphor NPS 25, and mixtures thereof.
  • sorbates for example polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80 and / or polysorbate 85, for example available under the trade name Tween, sodium dodecylsul
  • the at least one, preferably present, emulsifier is in an amount of, for example, 0.001 to 5 wt .-%, preferably 0.2 to 4 wt .-%, particularly preferably 1, 5 to 2.5 wt .-%, each based on the entire continuous, aqueous phase used.
  • Water is in the continuous, aqueous phase in an amount of, for example, 95 to 99.8 wt .-%, preferably 96 to 99 wt .-%, particularly preferably 97.5 to 98.5 wt .-%, each based on the entire continuous, aqueous phase, before.
  • the sum of the amount of at least one emulsifier and water is preferably 100% by weight.
  • the preparation of the emulsion in step (A) of the process according to the invention can be carried out by all methods known to the person skilled in the art, for example separate preparation of the disperse phase (I) by mixing the individual components, preparation of the continuous, aqueous phase (II) by mixing the individual Components, and combining the two phases (I) and (II), preferably with rotor-stator machines with known in the art devices, particularly preferably at speeds of at least 100 U / min, preferably at least 1000 U / min. More preferably, in step (A), ultrasound and high pressure homogenization are used to provide the emulsion, more preferably, high pressure homogenization is employed
  • Ultrasound is known to those skilled in the art as an efficient emulsification method, especially for low-viscosity disperse phases, see, for example, S. Bechtel et al., Chemie Ingenieurtechnik, 71, (8), 810-817, 1999, S. Bechtel et al., Chemie Ingenieur Technique, 72, (5), 450-459, 2000, O. Behrend, Mechanical Ultrasonic Emulsification., Dissertation, (2015) Düsseldorf (TH), 2002 or S. Kentish et al. innovative Food Science & Emerging Technologies, 9, (2), 170-175, 2008.
  • High-pressure homogenization is a process known to those skilled in the art for homogenizing emulsions, for example by introducing the pre-emulsion under pressure into a homogenizing valve which has a homogenizing opening, see, for example, DE 26 33 288 and S. Freitas et al., Ultrasonics Sonochemistry, 13, (1), 76-85, 2006.
  • the present invention therefore preferably relates to the process according to the invention, wherein in step (A) the emulsion is provided by the use of high-pressure homogenization, ultrasound and / or stirring.
  • step (A) is preferably carried out at a temperature of -10 to 60 ° C., preferably -5 to 40 ° C., particularly preferably 0 to 25 ° C.
  • the present invention therefore preferably relates to the inventive method, wherein
  • step (A) an emulsion comprising the abovementioned disperse phase (I) and a continuous, aqueous phase (II) in emulsified form is present.
  • This is preferably converted according to the invention directly into step (B) of the process according to the invention.
  • Step (B): Step (B) of the process of the invention comprises adding at least one precursor compound of the at least one inorganic material to the emulsion of step (A), so that in the disperse phase, the at least one inorganic material is formed by precipitation.
  • the at least one precursor compound of the at least one inorganic material it is possible to use any compound known to those skilled in the art in the disperse phase (I) by reaction with the at least one compound which effects the precipitation of the at least one inorganic material reacting in the hybrid nanoparticle according to the invention present at least one inorganic material.
  • the at least one inorganic material is preferably at least one metal compound, wherein the metal is more preferably selected from the group consisting of zinc, iron, titanium, tin, indium, zirconium, cerium and mixtures thereof.
  • the at least one inorganic material selected in step (B) is particularly preferably selected from the group of metal oxides, particularly preferably selected from the group consisting of zinc oxide, iron oxide, titanium dioxide, tin oxide, indium oxide, zirconium dioxide, cerium oxide and mixtures thereof.
  • the present invention therefore preferably relates to the process according to the invention, wherein the at least one inorganic material is selected from the group of metal oxides, more preferably selected from the group consisting of zinc oxide, iron oxide, titanium dioxide, tin oxide, indium oxide, zirconium dioxide, cerium oxide and mixtures thereof.
  • the at least one inorganic material is selected from the group of metal oxides, more preferably selected from the group consisting of zinc oxide, iron oxide, titanium dioxide, tin oxide, indium oxide, zirconium dioxide, cerium oxide and mixtures thereof.
  • Corresponding precursor compounds of the at least one inorganic material which are added in step (B) of the process according to the invention are therefore preferably selected from water-soluble compounds which contain the corresponding metal cation, for example selected from the group of the corresponding halides, carbonates, sulfates, phosphates , Acetates, nitrates, alkoxides and mixtures thereof.
  • Particularly preferred sulfates are used, more preferably zinc and / or iron (II) sulfate.
  • These metal compounds are preferably added as an aqueous solution.
  • the at least one precursor compound of the at least one inorganic material is preferably used according to the invention in an amount of 0.001 to 2% by weight, particularly preferably 0.1 to 1% by weight, very particularly preferably 0.1 to 0.5% by weight. , in each case based on the total emulsion added.
  • step (B) is preferably carried out at a temperature of -10 to 60 ° C., preferably -5 to 40 ° C., particularly preferably 0 to 25 ° C.
  • the optional step (C) of the process of the invention comprises the addition of at least one compound which effects the polymerization of the at least one precursor compound of the at least one polymeric organic material, if not in step (A).
  • step (C) preference is given to using at least one compound which effects the polymerization of the at least one precursor compound of the at least one polymeric organic material selected from the group consisting of water-soluble compounds, for example potassium peroxodisulfate, peroxides (eg hydrogen peroxide).
  • water-soluble compounds for example potassium peroxodisulfate, peroxides (eg hydrogen peroxide).
  • Azo initiators eg, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane]
  • 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate
  • 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] and mixtures thereof.
  • Step (D) of the process of the invention comprises the polymerization of the at least one precursor compound of the at least one polymeric, organic material.
  • step (D) is preferably heated and / or irradiated with light, in particular UV light, to effect the polymerization bring about.
  • step (D) is preferably carried out at a temperature of from 40 to 100.degree. C., preferably from 50 to 90.degree. C., particularly preferably from 60 to 80.degree.
  • the present invention also relates to nanoparticles which can be prepared, preferably prepared, by the process according to the invention.
  • an inorganic material is first formed in the disperse phase of an emulsion and in a further step this disperse phase is polymerized to a polymer, it is possible to provide nanoparticles according to the invention, which are characterized by a particularly homogeneous distribution of the inorganic material in distinguish the polymeric, organic material.
  • nanoparticles are formed with a core-shell structure, wherein the at least one inorganic material in the Core and the at least one polymeric, organic material in the shell is present.
  • nanoparticles are obtained which are distinguished from one another by a very homogeneous distribution of inorganic and polymeric, organic materials.
  • the nanoparticles according to the invention can be used, for example, in optical, electronic, chemical, agrochemical, medical-technical, pharmaceutical and / or biotechnological systems or for the administration of at least one active substance.
  • the present invention therefore furthermore relates to the use of a nanoparticle according to the invention in optical, electronic, chemical, agrochemical, medical-technical, pharmaceutical and / or biotechnological systems or for the administration of at least one active substance.
  • the emulsion consisted of 90% by weight of continuous aqueous and 10% by weight of disperse phase.
  • the continuous phase itself was prepared from 98% by weight demineralized water and 2% by weight Tween 80 (Karl Roth GmbH and Co.).
  • the composition of the disperse phase was 93.75% by weight of methyl methacrylate (MMA, Merck KGaA), 3.91% by weight of hexadecane as the osmotic reagent and 2.34% by weight of dimethyl 2,2'-azobisisobutyl nitrate (V601, Wako Chemicals GmbH) or 2,2'-azoisobutyronitrile (AI BN), Wako Chemicals GmbH) as an initiator.
  • MMA methyl methacrylate
  • V601 dimethyl 2,2'-azobisisobutyl nitrate
  • AI BN 2,2'-azoisobutyronitrile
  • the pre-emulsion was further sonicated.
  • An ultrasound processor UP 200s Hielscher Ultrasonics GmbH
  • the reaction solution was cooled in an ice bath.
  • 6 ml of 0.1 molar ZnSC (Merck KGaA) or FeSC (Merck KGaA) were added to the emulsion.
  • the reaction solution was placed in a water bath at 72 ° C. for 4 hours.
  • the emulsions were characterized before and after the polymerization by dynamic light scattering (Namotrec, Microtrec, USA). The conversions of the monomers to polymers were determined gravimetrically. The hybrid polymer particles were further analyzed by TEM with a LE0922, Omega. The conversions of monomer to polymer for the initiators AI BN and V601 and the precursor compounds FeS0 4 and ZnS0 4 are shown in Table 1 below.
  • FIG. 1 shows TEM images of the individual experiments.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Colloid Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de production de nanoparticules hybrides contenant au moins un matériau inorganique et au moins un matériau polymère organique, comportant au moins les étapes: (A) préparation d'une émulsion comportant une phase dispersée (I) contenant au moins un composé précurseur dudit matériau polymère organique et au moins un composé qui provoque la précipitation dudit matériau inorganique, une phase aqueuse continue (II) et éventuellement au moins un composé qui provoque la polymérisation dudit composé précurseur, celui-ci étant présent dans la phase dispersée (I), dans la phase aqueuse continue (II) ou dans les deux phases (I) et (II), (B) ajout d'au moins un composé précurseur dudit matériau inorganique à l'émulsion de l'étape (A) afin que ledit matériau inorganique se forme par précipitation dans la phase dispersée, (C) éventuellement ajout d'au moins un composé qui provoque la polymérisation dudit composé précurseur dudit matériau polymère organique si celle-ci n'a pas eu lieu à l'étape (A), et (D) polymérisation dudit composé précurseur dudit matériau polymère organique. La présente invention concerne également des nanoparticules pouvant être produites par le procédé selon l'invention ainsi que l'utilisation d'une nanoparticule selon l'invention dans des systèmes optiques, électroniques, chimiques, agrochimiques, médicotechniques, pharmaceutiques et/ou biotechnologiques ou pour l'administration d'au moins un principe actif.
EP13765300.2A 2012-09-10 2013-09-09 Précipitation de nanoparticules dans des monomères pour la production de particules hybrides Withdrawn EP2892932A1 (fr)

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US201261698739P 2012-09-10 2012-09-10
EP12183721 2012-09-10
PCT/EP2013/068580 WO2014037554A1 (fr) 2012-09-10 2013-09-09 Précipitation de nanoparticules dans des monomères pour la production de particules hybrides
EP13765300.2A EP2892932A1 (fr) 2012-09-10 2013-09-09 Précipitation de nanoparticules dans des monomères pour la production de particules hybrides

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CN (1) CN104781285A (fr)
AU (1) AU2013311595A1 (fr)
CA (1) CA2884276A1 (fr)
IL (1) IL237553A0 (fr)
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AU2018340885A1 (en) 2017-09-26 2020-05-07 National Research Council Of Canada Polymer film-metal composites
CN109092221A (zh) * 2018-09-01 2018-12-28 兰州理工大学 聚丙烯酰胺包覆的四氧化三铁粒子材料的制备方法及其应用

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PH12015500454A1 (en) 2015-04-20
US20150225532A1 (en) 2015-08-13
WO2014037554A1 (fr) 2014-03-13
RU2015113030A (ru) 2016-10-27
JP2015527473A (ja) 2015-09-17
IL237553A0 (en) 2015-04-30
KR20150054869A (ko) 2015-05-20
MX2015003082A (es) 2015-11-09
CA2884276A1 (fr) 2014-03-13
CN104781285A (zh) 2015-07-15
AU2013311595A1 (en) 2015-04-02

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