EP3500610A1 - Magnetische nanokapseln als thermolatente polymerisationskatalysatoren oder -initiatoren - Google Patents
Magnetische nanokapseln als thermolatente polymerisationskatalysatoren oder -initiatorenInfo
- Publication number
- EP3500610A1 EP3500610A1 EP17755471.4A EP17755471A EP3500610A1 EP 3500610 A1 EP3500610 A1 EP 3500610A1 EP 17755471 A EP17755471 A EP 17755471A EP 3500610 A1 EP3500610 A1 EP 3500610A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mpa
- monomer
- less
- reaction mixture
- nanocapsules
- 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- Withdrawn
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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- 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
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- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
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- C09K2200/0239—Oxides, hydroxides, carbonates
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- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
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- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0306—Metals or alloys, e.g. LAVES phase alloys of the MgCu2-type
Definitions
- the present invention relates to a process for the preparation of special nanocapsules, which can be used as thermolatent polymerization catalysts / initiators, in particular for the polymerization of polyurethanes.
- the invention further relates to the nanocapsules prepared by the described methods, their use and agents containing these nanocapsules.
- Polyurethanes are widely used materials that find application in a variety of fields.
- DBTL dibutyltin dilaurate
- Zinnndodekanoat used.
- a complete abandonment of tin-based catalyst systems would be particularly desirable from both ecological and health aspects.
- thermolatent catalysts i.
- Microcapsules are already well established in the art. Microcapsules have a size of 1 to 1000 ⁇ and are usually opened mechanically by breaking, with the content is released.
- a disadvantage of microcapsules is that they tend in the application for coagulation or sedimentation and their use is limited to applications in which the size of the capsules does not adversely affect, such as in infusion processes in the composite area, where the as a gain fibers used the complete Penetration of a gel with a microcapsule-containing polymer resin can prevent by retaining the microcapsules.
- Nanocapsules represent an alternative to the known microcapsules. Due to their size in the range of only 50 to 500 nm (z-average from dynamic light scattering (DLS)), these capsules can not be mechanically opened by breaking open, but must be formulated in this way in that they open in response to certain signals or environmental conditions. However, it is difficult to achieve a high encapsulation efficiency with nanocapsules, which is due to the small size and the fact that the thin shell of the nanocapsules without special precautions or adjustments only very limited
- Diffusion barrier can serve.
- the object of the present invention was therefore to provide nanocapsules which overcome the existing disadvantages and are suitable as thermolatent catalysts.
- the present invention solves this problem by providing the nanocapsules in one step by means of a combined emulsion / miniemulsion polymerization approach
- Monomer mixture and to be encapsulated magnetic nanoparticles and optionally a hydrophobic release agent can be produced.
- the nanocapsules obtainable in this way have different morphologies, the polymer formed from the monomers forming a shell or a matrix, and the magnetic nanoparticles and optionally the release agent forming the core or embedded in the polymer matrix become.
- the magnetic nanoparticles are able to catalyze the polyaddition reaction of compounds with isocyanate groups and NCO-reactive groups to form polyurethanes. For this reason, the use of customary catalyst / initiator substances, in particular tin-based catalyst / initiator substances, can be completely dispensed with.
- the nanocapsules thus obtainable are thermolatent, i.
- the content of the nanocapsules can be released controlled by increasing the temperature.
- the release can also take place via alternative mechanisms.
- the substances contained in the core of the nanocapsules at elevated temperature are themselves sufficiently compatible with the capsule shell to overcome the nanocapsule shell barrier (but at the temperatures used in the nanocapsule shell)
- Encapsulation and storage used are sufficiently incompatible to allow encapsulation and prevent premature release).
- the magnetic nanoparticles contained in the nanocapsules according to the invention by applying a heated external magnetic field according to the induction principle.
- a heated external magnetic field according to the induction principle By such heating of the nanocapsules above the glass transition temperature of the polymer shell, it becomes permeable or breaks up and the content of the nanocapsules localized in the core or in the polymer matrix is released in a targeted manner. Consequently, even in this case, the nanocapsules are sufficiently stable at temperatures prevailing during encapsulation and storage, thereby preventing premature release.
- a release agent is used, which swells at elevated temperature, the capsule shell and thus makes the contents of the capsule, permeable.
- the elevated temperature release agent is sufficiently compatible with the capsule shell to have a softening effect but sufficiently incompatible at the temperatures used in manufacture and storage to allow for efficient encapsulation.
- a blowing agent is used as the release agent, wherein the blowing agent is chosen such that it vaporizes at a fixed temperature and, due to the increasing pressure inside the nanocapsules, breaks them up, thereby liberating the catalyst.
- the nanocapsules are also characterized by a very high encapsulation efficiency and a high colloidal stability and prevent the release of the capsule contents under standard conditions very effectively, so that formulated PU materials have extended pot life.
- the invention relates to a process for the preparation of nanocapsules containing magnetic nanoparticles, characterized in that the process comprises: (A)
- Monomer mixture comprising:
- Divinylbenzene or a di- or triester of a C2-C10 polyol with ethylenic unsaturated C 3 -C 5 -carboxylic acids in particular a di- or triester of a C 2 -C 10 -alkanediol or triol with ethylenically unsaturated C 3 -C 5 -carboxylic acids;
- Reaction mixture based on the total weight of the reaction mixture, comprises:
- (b3) optionally 0.0 to 89.0% by weight of at least one hydrophobic release agent, wherein the release agent preferably has a Hansen parameter 5t of less than 20 MPa ' 2 ;
- (b4) optionally 0.0 to 10.0% by weight of at least one ultrahydrophobic compound other than the release agent, preferably an optionally fluorinated C12-28 hydrocarbon, more preferably a C14-26 alkane;
- reaction mixture comprising, based on the total weight of the reaction mixture:
- step (ii) optionally homogenizing the emulsion of step (i);
- a further aspect is directed to the nanocapsules obtainable by the methods described above and their use for catalyzing polymerization reactions, in particular of polyurethanes.
- Yet another aspect relates to agents and compositions containing the nanocapsules of the invention.
- At least one as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the kind of the ingredient and not to the absolute number of molecules. "At least one release agent” thus means, for example, at least one type of release agent, ie that kind of
- Release agent or a mixture of several different release agents can be used.
- weight information refers to all compounds of the specified type contained in the composition / mixture, ie Composition beyond the specified amount of the corresponding compounds addition no further compounds of this kind.
- Emmulsion or “miniemulsion” as used herein refers to an oil-in-water (O / W) emulsion in which the emulsified phase is in the form of droplets or particles, preferably of approximately spherical shape, in the continuous water phase available.
- the droplets / particles of a miniemulsion have an average size, with an approximately spherical shape an average diameter, in the size range of 50 to 500 nm, preferably 100 to 300 nm.
- nanocapsule refers to the emulsified polymerized particles prepared by the methods described herein, having the aforesaid average size in the range of 50 to 500 nm, preferably 100 to 300 nm Values refer to the z-average ("z-average") from dynamic light scattering according to ISO 22412: 2008.
- the term “nanocapsule” may refer to both a core-shell nanostructure in which a shell of polymers includes the magnetic nanoparticles as well as the remaining constituents of the present invention, as well as a matrix-like nanostructure In both cases, the magnetic nanoparticles as well as the remaining constituents of the respective nanostructure as defined herein are referred to as "encapsulated”.
- the monomers for the capsule shell are chosen such that the copolymer obtainable from the monomer mixture has a theoretical glass transition temperature T g of 95 ° C. or more, in particular 100 ° C. or more, more preferably 105 °, calculated analogously to the Fox equation C or and more.
- T g a theoretical glass transition temperature
- these T g values are preferred in order to ensure a sufficient barrier effect of the capsule shell.
- Glass transition temperature or " Tg” as used herein refers to the temperature at which a given polymer transitions from a solidified glassy state to a rubbery state and awakens polymer segment mobility. It is related to the Stiffness and the free volume of a polymer and can be experimentally known
- Measuring conditions or the thermal history of the polymer sample different glass transition temperatures can be obtained for an identical polymer system.
- Glass transition temperatures are therefore calculated theoretically analogous to the Fox equation, unless stated otherwise. In the following, the correspondingly calculated values of the glass transition temperature are sometimes also referred to as "estimated”.
- the capsule shell is widened more and more by increasing the mobility of the polymer and can thereby gradually lose at least part of their barrier effect, ie become more permeable to the encapsulated content.
- the thermolatency can thus be effected at least in part via the T g of the shell polymer and the raising of the temperature over the T g .
- the Fox equation states that the reciprocal glass transition temperature of a copolymer is calculated using the proportions by weight of the comonomers used and the glass transition temperatures of the corresponding homopolymers of the comonomers leaves:
- n represents the number of monomers used, i the running number via the monomers used, w, the mass fraction of the respective monomer i (in% by weight) and T the respective glass transition temperature of the homopolymer from the respective monomers i in K ( Kelvin).
- EHMA 2-ethylhexyl methacrylate
- IBOA Isobornyl acrylate
- IBOMA Isobornyl methacrylate
- T g 1 10 ° C
- the process described herein is based on a polymerization-induced phase separation determined by the interaction with water and in which a hydrophobic phase separation occurs
- nanocapsules by phase separation is based on the poor solubility of a polymer in a solution.
- an organic liquid to be included serve as a solvent for the monomers, wherein the same liquid after the
- Polymerization can no longer act as a solvent for the polymer.
- the Hansen parameter is des
- the Hansen parameter ot is preferably 23-28, preferably 24-27, more preferably 25-26.
- the Hansen parameter is always given herein in unit MPa ' 2 unless otherwise specified.
- the Hansen parameter is a widely used parameter in polymer chemistry for comparing the solubility or miscibility of various substances. This parameter was developed by Charles M. Hansen to predict the solubility of one material in another.
- the cohesive energy of a liquid is considered, which can be divided into at least three different forces or interactions: (a) dispersion forces between the molecules öd (b) Dipolar intermolecular forces between the molecules ⁇ ⁇ and (c) hydrogen bonds between the molecules 5h.
- Hansen parameter values given herein refer to the values as reported by Hansen in Hansen Solubility Parameters. A User's Handbook, Vol. 2, Taylor & Francis Group, Boca Raton, 2007, given or calculated, especially at room temperature (20 ° C). The determination of the Hansen parameters of Hansen
- Capsule shell takes place in particular as in Angew. Chem. Int. Ed. 2015, 54, 327-330.
- Hansen solubility parameters can be calculated with the volume fraction of the two solvents.
- This sphere represents the region in which the polymer is soluble (for linear polymers) or where it can be swelled (in the case of a crosslinked polymer network).
- Hansen solubility parameters can thus be determined by swelling experiments in solvents of known Hansen parameters. Is the polymer soluble or is it in the
- the Hansen parameter of the solvent is within the Lösigekkeitskugel of the polymer.
- the "distance" R a between the solubility parameters of these components can be calculated with the following equation (see CM Hansen, Hansen Solubility, Parameters A User 's Handbook, Vol. Taylor & Francis Group, Boca Raton, 2007):
- ⁇ Raf 4 ( ⁇ dS - 5dpf + ( ⁇ P s - 5 pP f + ⁇ 5 hS - Std
- High affinity or solubility presupposes that R a is less than R 0 .
- the polymer be poorly soluble in the respective one
- Hansen solubility parameters of the polymer used can be used to ensure good solubility of the polymer in the
- a RED value of 0 is found for no energy difference of the compared materials.
- a value less than one indicates high affinity, and a value greater than one indicates low affinity between the materials.
- a RED value less than or equal to one indicates solubility, a RED value greater than one indicates incompatibility and thus no mixture. Accordingly, preferably, a high RED value should result in comparing the core and shell substances to achieve phase separation during polymerization.
- the compound to be encapsulated or the mixture of compounds to be encapsulated satisfies the above relationship such that RED is> 1.
- Ro and R a are always given herein in unit MPa ' 2 unless otherwise specified.
- the mixture to be encapsulated i. the magnetic nanoparticles and optionally the polymerization catalyst, the release agent, in particular blowing agent, and / or the ultrahydrophobic compound, under homogenization and / or polymerization, preferably at room temperature (20 ° C) and atmospheric pressure (1013 mbar), preferably liquid "As used in this context, includes all flowable under the conditions mentioned substances, flowable homogeneous
- Monomer mixture in the mixture to be encapsulated under the emulsification / homogenization conditions are at least partially soluble.
- the monomer mixture can therefore be used as a solution of the monomers in at least one hydrophobic compound, for example the release agent or propellant.
- the release agent or propellant for example the release agent or propellant.
- step (i) emulsified / dispersed in the continuous phase.
- the magnetic nanoparticles are particulate aggregates, which in the
- the magnetic metal can be selected from the group consisting of Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, u, Mn, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, He, Tm, Lu, Ta, Os, Ir, Pt, Au, Eu, Sm, Yb. AI. Th and U are selected.
- it may also be a combination of the aforementioned metals. It is preferably Fe, Ni, La, Y. Mn or a combination of the aforementioned.
- it may also be a semi-metal, such as boron (B) act.
- the term “derivative" in this context refers to an alloy of one of the abovementioned metals with one or more other elements or an oxide or carbide of one of the abovementioned elements.
- the magnetic nanoparticles are capable of catalyzing or initiating the polymerization reaction of certain monomers or prepolymers, in particular the polyaddition reaction of compounds having isocyanate groups and NCO-reactive groups to give polyurethanes.
- the magnetic nanoparticles are magnetite nanoparticles.
- the magnetic nanoparticles have an average size, in an approximately spherical shape an average diameter, in the size range of> 1 nm preferably> 2 nm and / or ⁇ 50 nm, preferably ⁇ 25 nm, in particular ⁇ 15 nm, that is for example> 1 nm and ⁇ 50 nm, preferably> 1 nm and ⁇ 25 nm, particularly preferably> 2 nm and ⁇ 15 nm.
- the sizes of the particles can be determined, for example, by means of
- the magnetic nanoparticles of the present invention are superparamagnetic.
- the magnetic nanoparticles of the present invention have a magnetization with values in the range of> 60 emu / g, preferably> 70 emu / g, especially> 75 emu / g.
- the magnetic nanoparticles have a magnetization of at least 77 emu / g.
- Magnetization can be determined, for example, by means of a vibrating magnetometer (VSM) (Lu et al., Angew Chem Chem International Ed., 2007, 46, 1222-1244, McCollam et al., Review of Scientific Instruments 201, 1, 82, 053909, Foner , J. Appl. Phys., 1996, 79 (8), 4740-4745).
- VSM vibrating magnetometer
- the magnetic nanocapsules and / or the release agent In order for the magnetic nanocapsules and / or the release agent to be particularly effectively encapsulated, it is advantageous that they be hydrophobic so that they do not interact with the polymer formed from the monomers to unduly swell under synthetic and storage conditions thereby become more permeable.
- the surface of the magnetic nanoparticles be modified such that they are hydrophobic.
- Nanoparticles by the binding of ligands to the surface of the particles are all types of ligands capable of binding to the surface of the magnetic nanoparticles and at the same time a hydrophobic shell on their
- the surface of the magnetic nanoparticles according to the present invention is modified with a ligand having an HLB value of less than 10 as determined by the method described by Griffin (HLB Classification of surface active agents, J. Soc Cosmet. Chem. 1, 1949).
- the surface of the magnetic nanoparticles according to the present invention is modified with a ligand having a Hansen parameter 5t of less than 20, preferably less than 19, in particular less than 15; and / or has a Hansen parameter 5h of less than 12, preferably less than 10, more preferably less than 6, in particular less than 2.
- the ligand may have a Hansen parameter 5h of zero.
- the ligand satisfies the above relationship between Hansen parameters of the shell polymer and Hansen parameters of the ligand or mixture of ligand and release agent, and, if present,
- Catalyst / initiator such that RED> 1.
- modified nanoparticles are referred to as hydrophobized nanoparticles.
- the surface of the magnetic nanoparticles is modified with at least one saturated or unsaturated fatty acid having from 1 to 30 carbon atoms.
- saturated or unsaturated fatty acid having from 1 to 30 carbon atoms.
- exemplary in this connection are palmitoleic acid, oleic acid,
- Petroselinic acid Petroselinic acid, vaccenic acid, gadoleic acid, iscosenoic acid, cateloic acid, erucic acid,
- the surface is modified with a saturated or unsaturated fatty acid having a Hansen parameter 5t of less than 20, preferably less than 19, especially less than 15; and / or has a Hansen parameter 5h of less than 12, preferably less than 10, more preferably less than 6, in particular less than 2.
- the fatty acid satisfies the above relationship between Hansen parameters of the shell polymer and Hansen parameters of the fatty acid or mixture of fatty acid and release agent and, if present, catalyst / initiator such that RED is> 1.
- the surface of the magnetic nanoparticles is modified with oleic acid.
- the nanocapsules according to the invention may, in addition to the magnetic nanoparticles, which catalyze or initiate the polymerization reaction of certain monomers or prepolymers, in particular the polyaddition reaction of
- Compounds with isocyanate groups and NCO-reactive groups to polyurethanes additionally comprise at least one further polymerization catalyst or initiator.
- the at least one further catalyst / initiator compound has a Hansen parameter 5t of less than 20, preferably less than 19, in particular less than 15; and / or has a Hansen parameter 5h of less than 12, preferably less than 10, more preferably less than 6, in particular less than 2.
- the at least one catalyst / initiator may have a Hansen parameter 5h of zero.
- the catalyst / initiator compound especially when used without a release agent, satisfies the above relationship between Hansen parameters of the shell polymer and Hansen's Parameters of the catalyst / initiator such that RED is> 1.
- hydrophobic compounds i. the release agent, the catalyst / initiator and the ultrahydrophobic compound, not severely interfering
- hydrophobic compounds are therefore preferably inert under the conditions employed to the monomers and the reactants used in the polymerization (with the exception of deliberately used reactive release agents, which are described in more detail below).
- the hydrophobic compounds described above have an HLB value less than 10, as determined by the method described by Griffin (Classification of surface active agents by HLB, J. Soc. Cosmet. Chem., 1, 1949).
- a compound to be encapsulated can be considered to be excessively disturbing in the polymerization if, even upon post-polymerization or post-polymerization (see description below), a total monomer conversion of 80%, preferably 90% and more preferably 95% is not exceeded.
- Determination method is for example HPLC
- the (headspace) gas chromatography can serve as a determination method, which can also be used to determine the encapsulation efficiency.
- this method not only allows the quantitative determination of the release kinetics, but also the determination of the conversion of most monomers. In some cases not all used
- Comonomers can be measured by chromatographic methods (difficult determination of the total monomer conversion), the quantitative determination of individual comonomers is sufficient, which make up cumulatively at least 50% of the total monomer composition.
- a compound to be encapsulated is considered to be excessively disturbing if the cumulative conversion of at least 50% of the monomers used is ⁇ 80%, preferably ⁇ 90% and particularly preferably ⁇ 95%.
- the at least one additional catalyst or initiator is a compound that can also catalyze or initiate the polymerization reaction of certain monomers or prepolymers.
- It may be, for example, known olefin catalysts, including metallocenes and ligands / complex compounds containing, for example, lanthanides, actinides, titanium, chromium, vanadium, cobalt, nickel, zirconium and / or iron, organometallic compounds, such as organic compounds on tin, Bismuth, or Titanium base, metathesis catalysts (Schröck, Grubbs, molybdenum, ruthenium), or to organic compounds such as organic peroxides (such as those used as crosslinking peroxides under the trade names Perkadox® and Trigonox® by Akzo Nobel NV or Luperox® from Sigma Aldrich available) or tertiary amines, such as DABCO, DBU act.
- Preferred organometallic compounds are thiolates, for example
- Mercaptide of tin also preferred are halls (bis (salicylidene) ethylenediamine) and its derivatives, as described, for example, in Komatsu et al. (2008) Warden (Komatsu (2008) "Thermally latent reaction of hemiacetal ester with epoxides catalyzed by recyclable polymeric catalyst of salen-zinc complex and polyurethane main chain.” Journal of Polymer Science Part A: Polymer Chemistry 46 (1 1) : 3673-3681). Particular preference is given to catalysts for the synthesis of polyurethanes, for example organotin compounds, such as DBTL
- the at least one additional catalyst or initiator is a compound that is not tin-based.
- Catalyst / initiator is also not a catalyst / initiator for the polymerization of the monomers forming the capsule shell, i. different from such a catalyst / initiator.
- the at least one further catalyst / initiator compound is a hydrophobic compound, i. has a Hansen parameter as indicated above.
- the use of a release agent can be dispensed with. The release mechanism is then based on the one hand, that the nanocapsules depending on the
- Glass transition temperature T g of the copolymer are temperature-sensitive. Increasing the temperature leads to a higher mobility of the polymer chains in the shell and thereby to a widening of the polymer shell (increase in the free volume), which thereby becomes more permeable. On the other hand, then at elevated temperature and the catalyst / initiator has a softening effect on the capsule shell. However, it is preferred that the
- Catalyst / initiator is used together with a release agent containing this
- Nanocapsules which according to the present invention do not comprise catalytically active magnetic nanoparticles preferably have at least one polymerization catalyst or initiator (b2).
- the at least one polymerization catalyst or initiator (b2) is preferably contained in the nanocapsules in particular if the nanocapsules do not comprise magnetite nanoparticles, for example no hydrophobized magnetite nanoparticles, for example no magnetite nanoparticles hydrophobized with oleic acid.
- Catalyst / initiator is sufficiently soluble therein.
- the solubility for liquid compounds is preferably 20 g / l at room temperature (20 ° C) or solid compound at a temperature corresponding to the melting temperature of the compound T m + 20 ° C.
- the melting temperature can be determined according to the standard DIN EN ISO 1 1357-3: 2013-04 by means of DSC at a heating rate of 10 K / min.
- a Metrohm 662 photometer equipped with a probe can be used to determine the light transmittance. For the measurement, visible light (entire spectrum) is then guided via optical fibers to the probe, which is immersed in the liquid sample.
- the light is emitted from the probe tip, travels through the sample solution, is reflected by a mirror, and then directed to the detector via optical fibers.
- an optical filter can be used to allow the selective measurement of a particular wavelength. For such measurements, a wavelength of 600 nm can be used.
- An Ahlborn Almemo Multimeter was used to digitally record the transmissivity (analog output of the photometer) and a light transmittance of ⁇ 98% (at the chosen wavelength) was assumed to be complete solubility.
- the wavelength measurement range should be set so that the measurement is performed in a region of minimum excitation.
- the solubility can be determined gravimetrically (dry weight of a saturated solution). Further quantitative methods, eg based on chromatography or spectroscopy, are known to the expert and / or can be borrowed from the literature.
- the release agent is also hydrophobic.
- the release agent has an HLB value of less than 10, as determined by the method described by Griffin (Griffin, W.C.: Classification of surface active agents by HLB, J. Soc. Cosmet. Chem. 1, 1949).
- the release agent has a Hansen parameter 5t of less than 20, more preferably less than 19, even more preferably less than 15; and / or a Hansen parameter 5h of less than 12, preferably less than 10, more preferably less than 6, in particular less than 2 has.
- the at least one release agent may have a Hansen parameter 5h of zero.
- release agent satisfies the above relationship between Hansen parameters of the shell polymer and Hansen parameters of the release agent or mixture of release agent and catalyst / initiator such that RED is> 1.
- the release agent is below
- Homogenization and / or polymerization conditions preferably at room temperature (20 ° C) and atmospheric pressure (1013 mbar), liquid.
- the release agent may be a reactive release agent that is at least partially polymerized in the catalyst-mediated polymerization after the capsules are broken.
- suitable compounds include, but are not limited to, polyfunctional nucleophilic compounds such as hydroxyl group-containing compounds, particularly the various polyols including polyether polyols such as polypropylene glycol, polytetrahydrofuran, polyesters, and also polyamides and polydimethylsiloxane, as well as castor oil, cardanol derivatives, where no phenolic
- Hydroxyl groups are present, and other long-chain hydrophobic polyols and monoalcohols and (hydrophobic) epoxy resins.
- the release agent is a hydrophobic blowing agent, preferably a hydrocarbon, having a boiling point of 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
- the stated boiling point refers to the boiling point under standard conditions, i. at normal pressure (1013 mbar).
- the blowing agent is in various embodiments a Ce- ⁇ hydrocarbon, preferably a Ce-10 alkane, in particular isooctane (2,2,4-trimethylpentane), or a mixture of the aforementioned compounds.
- the propellant is preferably liquid at standard conditions and may serve to dissolve the monomers and, optionally, the catalyst compound therein.
- the specified boiling points make it possible to break up the nanocapsules by heating to temperatures above these boiling points, since the propellant then evaporates and the increasing pressure causes the nanocapsules to burst open.
- Catalysts / initiators Such embodiments are also within the scope of the invention.
- a stabilized emulsion is prepared.
- the emulsion contains the monomer mixture described above and at least one stabilizer, in particular a surfactant, the magnetic nanoparticles, optionally the
- the aqueous solvent contains as main component (more than 50,
- the aqueous solvent may contain one or more nonaqueous solvents, for example selected from monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the given concentration ranges.
- These additional solvents are preferably selected from ethanol, n- or isopropanol, butanol, glycol, propanediol or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether .
- such solvents can be used in amounts of between 0.5 and 35% by weight, but preferably less than 30% by weight and in particular less than 25% by weight.
- the monomers used in the processes described are in particular ethylenically unsaturated carboxylic acids and their alkyl esters.
- the at least one monoethylenically unsaturated C3-C5 carboxylic acid monomer is selected from methacrylic acid (MAA), acrylic acid (AA),
- Fumaric acid methylmaleic acid, maleic acid, itaconic acid or mixtures of two or more thereof. Particularly preferred are methacrylic acid (MAA), acrylic acid (AA) or mixtures thereof. Most preferred is methacrylic acid. These are, based on the monomer mixture, in particular in amounts of 2.5 to 19 wt .-%, preferably 5 to 12 wt .-%.
- the at least one monoethylenically unsaturated C3-5-carboxylic acid Ci-io-alkyl ester monomer is an acrylic acid or methacrylic acid alkyl ester or a mixture thereof.
- methacrylic acid-C 1 -5-alkyl ester monomers in particular methyl methacrylate (MMA), n-butyl methacrylate (BMA) or a mixture thereof.
- MMA methyl methacrylate
- BMA n-butyl methacrylate
- Very particular preference is given to a mixture of methyl methacrylate and
- Methacrylic acid n-butyl ester in particular in a weight ratio of 3.5: 1 to 16: 1, preferably 6: 1 to 16: 1.
- the alkyl radicals may generally be straight-chain or branched, unless specified specifically.
- These monomers are, based on the monomer mixture, in particular in amounts of 76 to 97.5 wt .-%, preferably 85 to 95 wt .-%.
- the monomer bearing at least two ethylenically unsaturated groups may generally be any compound bearing two ethylenically unsaturated groups, for example two vinyl groups.
- suitable compounds include, but are not limited to, divinyl aromatics, such as, in particular, divinylbenzenes or multiple esters of a polyol with ethylenically unsaturated carboxylic acids, especially di- or triesters of a C 2 -C 10 polyol with ethylenically unsaturated C 3 -C 8 carboxylic acids.
- the latter are in various embodiments diester of methacrylic acid or acrylic acid with 1, 3-propanediol, 1, 4-butanediol or 1, 5-pentanediol, especially a methacrylic acid ester of 1, 4-butanediol.
- the abovementioned compounds having at least two ethylenically unsaturated groups serve as crosslinkers in the monomer mixtures.
- the crosslinkers are based on the
- Monomer mixture in amounts of up to 0 to 5 wt .-%, preferably up to 4.5 wt .-%, more preferably used to 4 wt .-%.
- an ultrahydrophobic compound in particular a C12-28 hydrocarbon, more preferably a Cu-26 alkane , such as hexadecane, are emulsified in the continuous phase.
- a C12-28 hydrocarbon more preferably a Cu-26 alkane , such as hexadecane
- Cu-26 monoalcohols or monocarboxylic acids or fluorinated derivatives of the aforementioned may be suitable.
- the catalyst can be present, for example, dissolved in these.
- the ultrahydrophobic compound may also incorporate a polymerizable into the capsule shell or matrix C12-28 hydrocarbyl, possible compounds include, but are not limited to, lauryl (meth) acrylate (LA or LMA), tetradecyl (meth) acrylate (TDA or TDMA),
- ultrahydrophobic compounds are compounds other than the release agent, typically those which have a boiling point> 200 ° C under standard conditions.
- "Ultra-hydrophobic" as used herein in connection with the compounds described above means that the corresponding compound has a solubility in water at 60 ° C of less than 0.001% by weight as determined by the method described by Chai et al
- the monomer mixture in step (i) it is also possible with the monomer mixture in step (i) to emulsify further polymerizable compounds, for example vinylically unsaturated monomers, in particular styrene, into the continuous phase.
- additional polymerizable compounds for example vinylically unsaturated monomers, in particular styrene
- the amount is not more than 50% by weight based on the monomer mixture as defined above.
- the monomer mixture used is a mixture of:
- Such mixtures give a polymer having the desired glass transition temperature (calculated as described above analogous to the Fox equation), for example of> 95 ° C., in particular> 100 ° C.
- these monomer mixtures are hydrophobic enough to give stable miniemulsion droplets.
- the emulsion 1 prepared in step (i) of the process according to the invention contains from 0 to 70.0% by weight, preferably from 1.0 to 30.0% by weight, more preferably from 0.1 to 15% by weight. % magnetic nanoparticles as defined above; From 0.0 to 70.0% by weight, preferably from 1.0 to 70.0% by weight, more preferably from 5.0 to 70.0% by weight of at least one A polymerization catalyst or initiator as defined above; 0.0 to 89.0 wt.%, Preferably 1.0 to 89.0 wt.%, More preferably 5.0 to 89.0 wt.%, Particularly preferably 10.0 to 89.0 wt.
- At least one hydrophobic releasing agent as defined above at least one hydrophobic releasing agent as defined above; and from 0.0 to 10.0% by weight, preferably from 1.0 to 10.0% by weight, in particular from 5.0 to 10.0% by weight, of at least one ultrahydrophobic compound other than the release agent.
- step (i) and optionally step (ii) of the method at least one stabilizer is further used.
- stabilizer refers to a class of
- the stabilizer molecules can be attached to the surface of the droplets or interact with this.
- Stabilizers are used, which can react covalently with the monomers used. If polymerizable stabilizers are used, they are not included in the calculation of the glass transition temperature analogous to the Fox equation (see above). Stabilizers generally contain a hydrophilic and a hydrophobic portion, wherein the hydrophobic part interacts with the droplet and the hydrophilic part is oriented towards the solvent.
- the stabilizers may be, for example, surfactants and may carry an electrical charge. In particular, they may be anionic surfactants, for example
- Alternative stabilizers that can be used in the methods described herein are known to those skilled in the art and include, for example, other known surfactants as well as polymeric protective colloids, such as e.g. Polyvinyl alcohol (PVOH) or polyvinylpyrrolidone (PVP).
- PVOH Polyvinyl alcohol
- PVP polyvinylpyrrolidone
- the blends described herein may also contain other protective colloids, such as hydrophobically modified polyvinyl alcohols,
- the total amount of stabilizer / surfactant is typically up to 30% by weight, preferably 0.1 to 10% by weight, more preferably 0.2 to 6% by weight, based on the total amount of Monomers or, if separate emulsions are used in the preparation of the hydrophobized magnetic nanoparticles.
- the stabilizer can be used in the form of an aqueous solution.
- This solution may be compositionally similar to the composition of the continuous phase as defined above.
- the preparation of the magnetic nanohybrid particles according to the invention takes place via a combined
- the first reaction mixture (a) becomes in step (i) by emulsifying the above-described components (a1), (a2) and (a3) into one
- the emulsion is prepared by mixing the respective different ingredients, for example with an Ultra-Turrax.
- step (ii) The preparation of a second reaction mixture (b) takes place in a step (ii) analogously to step (i) with the constituents (b1), (b2), (b3) and (b4) described above.
- reaction mixtures or miniemulsions thus obtained, i. the first miniemulgiere reaction mixture from step (i) and the second miniemulg Of reaction mixture from step (ii) are then combined together in a step (iii).
- the combining of the two mini-emulsions can mean a direct mixing together of the two miniemulsions. However, the combining of the two miniemulsions can also be done via the preparation of another miniemulsion.
- the preparation of the emulsion may also be accomplished by emulsifying the monomer mixture and all other ingredients, i. especially the components to be encapsulated, in a single step.
- the emulsion is in this case prepared by mixing the respective different constituents, for example with an Ultra-Turrax, and optionally subsequently
- the homogenization and thus the production of a miniemulsion is carried out by a high shear process, for example by means of a high pressure homogenizer, for example with an energy input in the range of 10 3 to 10 5 J per second per liter of emulsion and / or shear rates of at least 1,000,000 / s. Shear rates can be readily determined by one skilled in the art by known methods.
- the high shear process as used herein, may be by any known method of dispersing or emulsifying in a high shear field. Examples of suitable
- the polymerization is carried out according to the present invention with a suitable polymerization process, in particular by means of radical polymerization.
- polymerization initiators can be used.
- Useful initiators include, for example, thermally activatable, radiation-activatable, such as UV initiators, or redox-activatable, and are preferably selected from radical initiators.
- Suitable free radical initiators are known and available and include organic azo or peroxy compounds.
- the initiators are preferably water-soluble. When polymerization is initiated by a water-soluble initiator, free radicals are generated in the aqueous phase and diffuse to the water / monomer interface to initiate polymerization in the droplets.
- suitable initiators include peroxodisulfates, such as
- KPS Potassium peroxodisulfate
- the polymerization may be carried out at elevated temperature, for example at a temperature in the range of 10-90 ° C, preferably 20-80 ° C, more preferably 40-75 ° C and most preferably 60-75 ° C.
- the polymerization can take place over a period of 0.1 to 24 hours, preferably 0.5 to 12 hours, more preferably 2 to 6 hours.
- the polymerization takes place under conditions compatible with the encapsulated active substances.
- the amount of residual monomers can also be carried out chemically by post-polymerization, preferably by the use of redox initiators, such as those described in DE-A 44 35 423, DE-A 44 19 518 and DE-A 44 35 422 .
- Suitable oxidizers for post-polymerization include, without limitation: hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, or alkoxy peroxosulfates.
- Suitable reducing agents include, without Restriction: sodium disulfite, sodium bisulfite, sodium dithionite,
- the post-polymerization with a redox initiator can be carried out in a temperature range of 10 to 100 ° C, especially 20 to 90 ° C.
- the redox agents may be added independently or continuously over a period of 10 minutes to 4 hours.
- soluble salts of metals having different valences such as iron, copper or vanadium salts, may be added to the reaction mixture.
- complexing agents which keep the metal salts in solution under the reaction conditions are also added.
- a chain length regulator can be used.
- Suitable compounds are known in the art and include, for example, various thiols, e.g. 1-Dodecanethiol. In different
- Embodiments in particular use those chain length regulators which can be consumed (polymerized in) in a reaction to be catalysed by the magnetic nanohybrid particles according to the invention.
- the chain length regulators can be used in the necessary amounts to the chain length to the desired extent
- Typical amounts are in the range of 0, 1 to 5 wt .-%, preferably about 0.3 to 2.0 wt .-%, more preferably about 0.5 to 1, 0 wt .-% based on the
- the invention relates to the nanocapsules by means of herein
- magnetic nanoparticles may, in various embodiments, include magnetic nanoparticles, optionally one or more release agents, especially blowing agents, optionally one or more additional catalysts / initiators, and optionally one or more ultra hydrophobic compounds.
- the magnetic nanoparticles with oleic acid are hydrophobized magnetite nanoparticles and the optional blowing agent is isooctane and the ultrahydrophobic compound is hexadecane.
- the content of the nanocapsules of the invention can be released by increasing the temperature.
- this temperature - dependent release of the capsule contents can be induced by magnetically induced heating of the magnetic nanoparticles inside the
- Nanocapsules done. In addition to the increase in mobility of the polymer chains in the shell or matrix above the T g, either the barrier effect of the shell or matrix is weakened by increasing their compatibility with the encapsulated compounds swells and thereby widened or, in the event that a blowing agent is used, the polymer shell is broken and the contents released when the temperature rises above the boiling point of the blowing agent. In connection with the nanocapsules and because of interactions with the polymer, the release may also be necessary to select a temperature which is up to 50 ° C above the actual boiling point of the propellant.
- Nanocapsules described herein may find application in the catalysis of a variety of processes, particularly polymerization processes.
- Nanocapsules which, according to the present invention, comprise exclusively the magnetic nanoparticles, in particular oleic acid hydrophobized magnetite nanoparticles, as catalytically active constituents, ie comprise no further catalyst / initiator compound, are particularly suitable for use in conjunction with polyurethanes which are polymerized in controlled manner in the application should. Accordingly, such nanocapsules as constituents of numerous
- compositions containing such polyurethanes can be used. These may, for example, be adhesives or polyurethane-based coating agents. It is also conceivable to use nanocapsules according to the present invention containing titanium-based catalysts for condensation reactions, for example of silanes or silane-containing polymers. Further fields of application are the polymerization of epoxides, benzoxazines and metathesis systems. Particularly preferred is the use in crosslinking systems, such as elastomers and especially duromers. Generally close the
- Applications include adhesives, sealants, coatings and infusion resins.
- compositions containing the nanocapsules described herein thus further contain, in various embodiments, at least one polyisocyanate or NCO-functional prepolymer and at least one compound having at least two NCO-reactive groups, especially a polyol.
- the catalyst i.
- the magnetic nanoparticles and / or additional catalyst / initiator compounds then, upon release, catalyze the reaction between the isocyanate (NCO) groups and the NCO-reactive groups, typically hydroxyl groups, which react in a polyaddition to form urethane groups.
- the polyurethane polymers are formed from the monomers or prepolymers.
- prepolymers having NCO-reactive groups for example OH-functional prepolymers, can be used in addition to or instead of the NCO-functional prepolymers described.
- compositions can all be used in connection with the polyurethane synthesis commonly used compounds.
- the compositions may also contain other conventional ingredients of such agents.
- Iron (II) chloride tetrahydrate Merck,> 99%
- Iron (III) chloride hexahydrate VWR,> 99
- Magnetic nanocapsules with magnetite loading between 1% and 10% were prepared by a miniemulsion process.
- Figure 1 shows the morphology of sample MOA 10 at different resolutions.
- the capsules have a very high uniformity, as well as a core-shell structure.
- Figure 1 b further shows that magnetite particles are present in the nanocapsules.
- a miniemulsion A 0.769 g of MMA, 0.103 g of BMA and 0.103 g of MAA were mixed with 0.0256 g of the crosslinker BDDMA with 0.03 g of hexadecane.
- a solution of 24 g of distilled water and 10 mg of SDS was then added and homogenized for three minutes with an Ultraturax (16000 rpm) for the pre-emulsification.
- an Ultraturax (16000 rpm) for the pre-emulsification.
- the monomer-mine emulsion was then produced for 120 seconds (10 sec. Pulse, 5 sec. Pause) under ice-cooling.
- a miniemulsion B the amounts of hydrophobized iron oxide nanoparticles indicated in Table 2 were dispersed in isooctane in an ultrasonic bath for 30 minutes and, depending on the sample, mixed with 0.769 g of Fomrez. Subsequently, a solution of 24 g of distilled water and 25 mg of SDS was added. The biphasic system was miniemulgiert with a Branson Sonifier 450-D with V 2 inch tip for 180 s (10 s pulse, 5 s rest) with ice cooling.
- HMOA magnetic polymer / hybrid particles with high magnetite loading
- the two miniemulsions A and B prepared were placed in a 100 ml one-necked flask, stirred for 5 minutes at room temperature and treated with a solution of 0.5 g of distilled water and 20 mg of KPS. Finally, the mixture was heated to 80 ° C and polymerized with stirring for 8 h.
- the size of the particles determined by dynamic light scattering, amounts to 109 m with a polydispersity index of 0.19 for LMOA F and to 87 nm for HMOA F with a distribution of 0.14.
- Figure 2 shows the morphology of the capsules thus prepared, where a-c are the low-magnetic-content capsules (LMOA F) and d-e are the high-particle particles
- the morphology of the LMOA capsules without catalyst is similar to that of the catalytic, magnetic nanocapsules LMOA F ( Figure 4).
- the Magnetitanteil is sufficiently low, so that have formed uniform core-shell structures.
- the magnetite is distributed homogeneously in the polymer matrix as expected.
- the particle sizes are 104 nm with a polydispersity index of 0.19.
- the Hansen parameter ⁇ d of the polymer of the capsule shell is approximately 17 MPa 2
- the Hansen parameter ⁇ P is approximately 12 MPa 2
- the Hansen parameter is approximately 15 , 3 MPa 1 ' 2 .
- HMOA F high
- LMOA F low
- TGA measurements were performed and compared with the nanocapsules without magnetite particles.
- the nanocapsules without magnetite show a mass loss of about 21% at 120 ° C, which is due to the evaporation of the isooctane. For the magnetic nanocapsules, this loss of mass is not recognizable.
- the decomposition of organic material begins with LMOA F and HMOA F at approx. 150 ° C and with the nanocapsules without magnetite loading at approx. 300 ° C.
- the polymer content of the nanocapsules without magnetite loading is much higher than that of the magnetic nanocapsules. This is further illustrated by the comparison of residues, which are only 8% for nanocapsules without magnetite loading, 54% for LMOA F and 64% for HMOA F, due to the higher inorganic content in these samples.
- the residue of LMOA amounts to approx. 58%.
- the saturation magnetizations of the LMOA sample calculated from the hysteresis curve shown in Figure 5 are 48 emu / g and due to the presence of the polymer shell in comparison to the saturation magnetization of the pure magnetite nanoparticles slightly decreased.
- Therheology measurements were carried out under isothermal conditions at 50 ° C. and 120 ° C. and the curing reaction of the polyurethane composite was monitored.
- Thermolatent capsules without magnetite in the matrix serve as a reference.
- the curing reaction was monitored at constant temperature by measuring the complex viscosity, as shown in Figure 4.
- the samples with the non-magnetite nanocapsules and the LMOA F nanocapsules show a modest increase in viscosity over time.
- the final viscosity of the LMOA F is so low that processing of the components is still possible even after several hours under these conditions. Both samples show a nearly identical behavior.
- the catalyst concentration is the same in all three samples, the sample with HMOA F shows a completely different behavior.
- the final viscosity is two orders of magnitude higher, which could be due to the morphology of the particles. Due to the large amount of magnetite particles in the polymer no core-shell structures are formed, which is why the catalyst is not shielded by a barrier, but is distributed freely in the polymer. For this reason, it can more easily diffuse out of the polymer and catalyze the polyurethane reaction.
- the sample with the nanocapsules without magnetite has an induction phase of about 15 minutes before the curing reaction is abruptly catalyzed.
- the catalysis of the reaction also takes place abruptly, but the induction phase is significantly shorter with 10 minutes.
- the HMOA F capsules do not even show an induction phase, but catalyze the reaction immediately.
- One reason for this could be catalytic properties of oleic acid be, whereby the curing reaction is additionally accelerated. Therefore, the possible catalysis by magnetite is considered in more detail below.
- Magnetite concentration at this time amounts to 1% by weight of magnetite, based on the polyol, for all samples in order to ensure the comparability of the results.
- Figure 6d shows oleic acid as a reaction accelerator of curing.
- the oleic acid in contrast to the previously used heterogeneous catalysts is a homogeneous catalyst.
- concentration of oleic acid is the proportion attached to 1% by weight of magnetite. Again, no catalysis of the reaction takes place at 50 ° C. At 120 ° C, however, after an induction phase of about 20 minutes one abrupt catalysis of the reaction. Thus, the oleic acid contributes significantly to the acceleration of the reaction.
- thermolatent catalysis is suitable.
- the accelerating effect of the magnetic nanocapsules on the PU reaction seems to be mainly due to the oleic acid.
- the induction phase is 9 minutes shorter when using the LMOA capsules than with oleic acid catalysis.
- the oleic acid as a homogeneous catalyst would have to catalyze the reaction faster. The additional acceleration comes thus on the probability by the
- Figure 1 shows the morphology of the magnetic nanocapsules containing 10% by weight.
- Magnetite prepared via a miniemulsion in step (ii) of the process as described herein at various resolutions.
- Figure 2 shows the morphology of magnetic nanocapsules containing the catalyst Fomrez with 15 wt .-% and 46 wt .-% magnetite (Fig. 2a), 2b), 2c)) or 64 wt .-% magnetite (Fig. 2d) , 2e), 2f)).
- Figure 3 shows the morphology of the magnetic nanocapsules containing 58% by weight.
- LMOA Magnetite
- Figure 4 shows the time-dependent measurement of complex viscosity matrix-forming
- Figure 5 shows a VSM measurement of magnetic nanoparticles containing 58 wt% magnetite (LMOA).
- Figure 6 shows the time-dependent measurement of the complex viscosity of matrix-forming monomers at 50 ° C and 120 ° C of a) the pure matrix (castor oil and IPDI trimer), b) the matrix and magnetite with oleic acid functionalization, c) the matrix and magnetite without
- Oleic acid functionalization d) the matrix and oleic acid, e) the matrix and LMOA.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Polymerisation Methods In General (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
Claims
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EP16184291 | 2016-08-16 | ||
PCT/EP2017/070695 WO2018033550A1 (de) | 2016-08-16 | 2017-08-16 | Magnetische nanokapseln als thermolatente polymerisationskatalysatoren oder -initiatoren |
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EP (1) | EP3500610A1 (de) |
JP (1) | JP2019526435A (de) |
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CN (1) | CN109563233A (de) |
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US10457843B2 (en) | 2017-08-18 | 2019-10-29 | !Obac Ltd | Magnetic flooring system adhesive composition |
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NZ233481A (en) | 1989-05-30 | 1992-04-28 | Ppg Industries Inc | Water-based coating compositions having reduced organic solvent content comprising an aqueous dispersion of hydrophobic polymer microparticles |
DE4419518A1 (de) | 1994-06-03 | 1995-12-07 | Basf Ag | Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion |
DE4435423A1 (de) | 1994-10-04 | 1996-04-11 | Basf Ag | Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion |
DE4435422A1 (de) | 1994-10-04 | 1996-04-18 | Basf Ag | Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion |
DE19628142A1 (de) | 1996-07-12 | 1998-01-15 | Basf Ag | Verfahren zur Herstellung von wäßrigen Polymerdispersionen mit bimodaler Teilchengrößenverteilung |
US20060078741A1 (en) * | 2004-10-12 | 2006-04-13 | Ramalingam Balasubramaniam Jr | Laminating adhesives containing microencapsulated catalysts |
SG11201401013TA (en) * | 2011-09-30 | 2014-04-28 | Univ Singapore | Method of converting grease containing high content of free fatty acids to fatty acid esters and catalysts for use in said method |
JP2014156368A (ja) * | 2013-02-14 | 2014-08-28 | Toda Kogyo Corp | 複合磁性微粒子粉末、分散体 |
CN104403041A (zh) * | 2014-12-05 | 2015-03-11 | 厦门大学 | 具有Janus结构的pH响应型磁性复合微球及其制备方法 |
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