WO2019158642A1 - Liant de pétrole - Google Patents

Liant de pétrole Download PDF

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Publication number
WO2019158642A1
WO2019158642A1 PCT/EP2019/053662 EP2019053662W WO2019158642A1 WO 2019158642 A1 WO2019158642 A1 WO 2019158642A1 EP 2019053662 W EP2019053662 W EP 2019053662W WO 2019158642 A1 WO2019158642 A1 WO 2019158642A1
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WO
WIPO (PCT)
Prior art keywords
oil
polymer
foam
range
oil binder
Prior art date
Application number
PCT/EP2019/053662
Other languages
German (de)
English (en)
Inventor
Roland OBERHOFFER
Alexander Müller
Original Assignee
Sumteq Gmbh
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 Sumteq Gmbh filed Critical Sumteq Gmbh
Priority to EP19706461.1A priority Critical patent/EP3752571A1/fr
Publication of WO2019158642A1 publication Critical patent/WO2019158642A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/283—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum a discontinuous liquid phase emulsified in a continuous macromolecular phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/04—Starch derivatives
    • C08J2303/06—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene

Definitions

  • the invention relates to open-cell foam oil binders, a method for producing the oil binder, and a method for binding oil, a method for recovering the oil binder, and the use of the oil binder in a cleaning agent.
  • Capillarity or capillary effect (lat. Capillaris, concerning the hair) is the behavior of liquids which, when in contact with capillaries, eg. As narrow tubes, columns or cavities in solids show. These effects are caused by the surface tension of liquids themselves and the interfacial tension between liquids and the solid surface.
  • polystyrene foams are described in the literature as ideal thermal insulating materials, since due to the so-called Knudsen effect, the heat conduction of the trapped cell gas is significantly reduced in the nanopores.
  • the production of, for example, polystyrene foams is described in the prior art in various publications. This is either a particle foam technology in which the polymer particles are already impregnated in the production process with a low molecular weight blowing agent such as cyclopentane and only in the next step by tempering with superheated steam are foamed (discontinuous process). This is illustrated, for example, in the patent application DE 103 58 800 A1, in which case an additional ipsoidal geometry of the enclosed propellant is additionally described here.
  • the proportion of air or porosity should be at least 80% by volume of the foam.
  • pore size, homogeneity of the pores, and the foam density should be well matched.
  • Nanoporous polymer foams with low density have not yet been sufficiently produced (see DE 10 2013 223 391 A1).
  • the object of the present invention is to provide a technology in which, on the one hand, cavities / packages with very complex geometries, which can also be very fine, can be filled with nanoporous foam and, on the other hand, oil can be taken up more efficiently than before can.
  • the foam In order to obtain a high oil absorption capacity, the foam must provide the lowest possible density and, in order to bind the oil, have structures as small as possible, which show a high capillarity. In addition, the structure must be open-celled so that the oil can penetrate.
  • the object underlying the invention is achieved by means of open-cell foam oil binder, characterized in that The oil binder of an open-celled polymer foam with pore sizes in the median between 0.01 and 10 miti, preferably between 0.02 and 5 miti, more preferably between 0.03 and 2 pm.
  • This pore size in the context of the invention is the median of the measured pores.
  • the oil binder can be used to bind oil after accidents on land or water, to clean water or containers or to catch leak oil.
  • the oil-binding property of the foam can be used to simplify transport operations and storage.
  • the chemical properties of the oil are retained during the binding process, for example, so that, for example, a thermal utilization can be carried out without losses.
  • the term "oil” is referred to as a collective term for organic substances that can not be mixed with water (hydrophobic).
  • An open-cell polymer nanofoam has great potential to absorb and bind hydrophobic liquids such as diesel. Due to the small structures, the capillarity is very high and hydrophobic liquids are thus quickly absorbed on the one hand and very firmly bound on the other hand. Even an increased pressure load only leads to a small release of the absorbed oil.
  • polymer nanofoams clearly differ from the polymer microfoams known in the art. It is advantageous that the properties of the hydrophobic substances in the foam structures can also be used further. It is preferably as described a physically bound hydrophobic substance in the small structures of the foam. For example, possible phase transitions of the hydrophobic substances and the associated energy input or output can continue to be used.
  • phase change materials latent heat storage or phase change material PCM
  • phase change materials they use their latent heat of fusion, heat of solution or heat of absorption, which is considerably greater than the thermal energy which they can store due to the specific heat capacity.
  • the phase change takes place reversibly.
  • the phase transition temperature can, as described in the literature, be shifted by mixtures or addition of additives to other temperatures.
  • the phase transition temperature may also be a temperature range.
  • the median particle size of the powder / granules can be determined, for example, by a scanning electron micrograph and counting per area or by means of calipers insofar as the particles are large enough.
  • the particle size denotes the largest possible distance, which is possible by a straight line in the particle.
  • the primary beam voltage of the scanning electron microscope can be set to 5 kV, for example.
  • the surface can be coated with gold to avoid unwanted charging effects, or the median can be determined by sieving the powder / granules. This can be done, for example, by fractionation in a sieving tower.
  • the pore size or the median pore size can be determined, for example, by means of electron microscopy by a person skilled in the art for measuring pores of polymer foams, which also dominates electron microscopy, performing a cut / break through the material and on the cut surface 10 pm ⁇ 10 pm measures the pore size of those pores that are completely within this range.
  • the median pore size or the pore size of the foam for example, by a scanning electron micrograph and Counting per area to be determined. For this purpose, for example, the surface of a powder / granule particle can be observed on an area of 10 pm ⁇ 10 ⁇ m and then the pores are counted and measured. For example, with irregularly shaped pores, the smallest visible diameter of the respective pore can always be evaluated.
  • the primary beam voltage of the scanning electron microscope can be set to 5 kV, for example.
  • the surface can be coated with gold to avoid unwanted charging effects.
  • the pore size can be determined concretely as follows: In order to image the structure of the nanoporous materials produced, a fresh breaking edge can first be produced. The sample can then be fixed on the sample tray with the broken edge facing upwards. In order for the charge resulting during the measurement to be dissipated, silver-conducting lacquer can be used for the fixation. For example, before the recordings can be made, the sample is coated with gold to avoid local charging effects.
  • the coating system K950X is used with the sputtering additive K350 from EMITECH.
  • gold sputtering occurs, for example, at an argon pressure of about 10-2 mbar, with a current of 30 mA always being applied for 30 seconds.
  • the layer thickness of the gold layer applied in this way is, for example, approximately between 5 and 15 nm.
  • the electron micrographs are carried out, for example, on a device of the SUPRA 40 VP type from ZEISS. With this device acceleration voltages of up to 30 kV and a maximum resolution of 1.3 nm are possible.
  • the recordings are recorded, for example, at an acceleration voltage of 5 kV with the InLens detector.
  • the average pore diameter and the average web thickness of the nano- and microporous foams for example, an image taken with the described scanning electron microscope is selected, and at least 300 pores or webs are measured with the computer program Datinf Measure To ensure statistics.
  • pores can be semi-closed as well as open. For the latter, one can also imagine an open-pored, sponge-like network.
  • the oil binder voluntarily incorporates hydrophobic liquids (e.g., oil, diesel, waxes, paraffins (alkanes), fatty acids, etc.) into the air-filled cavities.
  • hydrophobic liquids e.g., oil, diesel, waxes, paraffins (alkanes), fatty acids, etc.
  • the oil binder is preferably particulate.
  • the particle size may preferably be in the median range of 1 ⁇ m to 5 cm.
  • the particle size may, however, especially preferably be in the median range from 2 to 500 ⁇ m or in the range from 0.5 to 3 cm.
  • the median can be determined, for example, by measuring 100 particles.
  • the particle size can be determined microscopically for larger particles with a caliper gauge and for smaller particles. For smaller particles, an electron microscope (as described below) can also be used.
  • the particles of the oil binder are preferably spherical.
  • the oil binder preferably has a bulk density in a range from 20 to 300 kg / m 3 , particularly preferably from 25 to 200 kg / m 3 , very particularly preferably from 30 to 150 kg / m 3 .
  • the oil binder preferably absorbs at least twice, more preferably at least 7 times, most preferably at least 10 times, the intrinsic weight of oil.
  • the polymer may preferably be functionalized and / or surface modified to alter the polarity.
  • the oil binder may also contain other materials that can bind oil.
  • the oil binder preferably contains more than 50% by weight of the powder / granules, very particularly preferably more than 80% by weight of the powder / granules.
  • the oil binder can also consist of powder / granules.
  • the oil binder can also absorb polar substances such as water as soon as the interfacial energy is compensated.
  • the oil binder is buoyant (water).
  • the oil binder is still buoyant after absorbing oil. It is assumed that the oil has a specific gravity of ⁇ 1000 g / m 3 .
  • the oil binder does not release more than 50% by weight of the oil absorbed.
  • the absorption capacity at a pressure load of more than 1 t / m 2 is preferably maintained to more than 50%.
  • the oil binder is preferably translucent by absorbing oil.
  • the oil binder is preferably combustible.
  • the median of the diameter of the pores of the foam is preferably in a range from 20 to 5000 nm, particularly preferably in a range from 30 to 2000 nm, very particularly preferably in a range from 50 to 1000 nm.
  • Preferably at least 75 vol. %, more preferably at least 85% by volume, most preferably at least 95% by volume, of the pores has a diameter in a range from 50 nm to 1000 nm, very particularly preferably in a range from 60 nm to 400 nm.
  • the foam is open-celled.
  • the powder / particle can also be used for applications such as oil removal in tanker accidents.
  • the particles (powder / particles) preferably have a BET specific surface area (gas adsorption) in a range from 3 to 500 m 2 / g, particularly preferably in a range from 10 to 450 m 2 / g and very particular. It preferably ranges from 20 to 400 m 2 / g.
  • This BET specific surface area can be achieved, for example, with a multipoint BET instrument be determined according to DIN-ISO 9277.
  • the powder / particle has a very high capillarity.
  • the powder / particle according to the invention can absorb about 5 to 20 times its own weight of hydrophobic liquids (eg diesel) and still floats on the water in the case of oil or diesel. This was determined as follows: (test according to LTwS No. 27 (as of June 1999) with test mixture A20 / NP II (corresponds to heating oil EL according to DIN 51603)).
  • the particle shape of the particles (powder / particles) are preferably spherical, edged or sharp-edged or edge-rounded in the sense of DIN EN ISO 14688.
  • the foam is preferably a polymer foam. Polymers are combustible due to the organic nature.
  • This polymer foam is preferably partially crosslinked. Preferably, the foam is a partially crosslinked polymer foam.
  • the volume expansion ratio (VER) of the polymer foam (for example, for polymers with densities of 900-1200 kg / m 3 ) is in a range of 4 to 30, more preferably in a range of 7 to 25.
  • VER volume expansion ratio
  • the density of the foam is in a range of 30 to 300 kg / m 3 , more preferably in a range of 40 to 200 kg / m 3 , most preferably in a range of 45 to 150 kg / m 3 .
  • the lower limit of the density of the polymer foam in conjunction with the aforementioned upper limit may be in ascending order of 20, 30, 40, and more preferably 50 kg / m 3 .
  • the upper limit of the density of the polymer foam in conjunction with the Lower bounds in ascending order of preference would be 250, 200, 175, and more preferably 150 kg / m 3 .
  • a factor (FOM) for pore diameters between 10 nm and 10 ⁇ m can be defined for the combination of density and pore size of the foams:
  • FOM (ln (dPore / 0.15 nm)) / VER where dPore (diameter of the pores in the median) carries the unit nanometer.
  • all foams with pore sizes of less than 10 miti from the prior art known hitherto have a factor FOM> 1.2.
  • the polymer foam according to the invention preferably has a factor FOM of less than 1.2. Regardless, the factor FOM is preferably at least 0.01.
  • a foam is based on an increase in volume during the production process (foaming process).
  • the polymer foam may preferably be a polystyrene foam, a polymethyl methacrylate foam, a polylactic acid foam, a polyvinyl chloride foam, a polyurethane foam, a polyethylene foam and / or a mixture and / or copolymer foam of these polymer foams.
  • styrene in the context of the present invention may be, for example, alkylstyrene, alkoxystyrene, halostyrene, dihalogenostyrene or divinylstyrene and in particular be selected from the group consisting of 4-bromostyrene, 4-methylstyrene, 4-ethylstyrene, 4-propylstyrene, 4-iso butyl-styrene, 4-methoxy-styrene, 4-ethoxy-styrene, 2-vinyl-6-bromonaphthalene, 2-vinyl-6-methylnaphthalene or 2-vinyl-6-methoxynaphthalene, p-chlorostyrene, 2,4- Dimethylstyrene, 4-vinylbiphenyl, vinylnaphthalene, vinylanthracene and / or mixtures thereof.
  • derivatives of methyl methacrylate may be, for example, acrylic acid, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, 1-ethoxy-1-propyl methacrylate, glycidyl methacrylate, 2-trimethylsilyloxyethyl methacrylate, 2, 2, 2
  • Trifluoroethyl methacrylate 4- (tetrahydro-2-pyranyloxy) benzyl methacrylate, lauryl methacrylate, ethoxy triethylene glycol methacrylate, butoxyethyl methacrylate, methoxyethoxyethyl methacrylate, sorbyl methacrylate, 2-acetoxyethyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, octyl methacrylate, methoxypolyethylene glycol methacrylate, ethoxyethyl methacrylate, tetrahydropyranyl methacrylate, t Butyl methacrylate and 2-dimethylaminoethyl methacrylate and / or mixtures thereof.
  • the polymer foam according to the invention can also be obtained by polymerization of any desired mixture of the abovementioned monomers.
  • a starter is included.
  • the initiator is a radical initiator which decomposes by thermal energy and thereby releases two radicals, such as e.g. Azobisisobutyronitrile (AIBN), dibenzoyl peroxide, dicumyl peroxide, peroxoketals.
  • AIBN Azobisisobutyronitrile
  • dibenzoyl peroxide dicumyl peroxide
  • peroxoketals e.g. Azobisisobutyronitrile
  • the theoretical degree of crosslinking is a quantitative measure for the characterization of polymeric networks. It is calculated as the quotient of the number of crosslinked basic building blocks and the number of moles of the basic building blocks present in this macromolecular network. It can be stated in percent (mole fraction).
  • the theoretical degree of networking of a network results from the formulation of the network.
  • this theoretical degree of crosslinking is almost never achieved, since not all crosslinkable building blocks find a reaction partner during network formation because of the spatial hindrance that occurs.
  • the theoretical degree of crosslinking of the polymer foam is preferably in a range of 0.005 mol% to 10 mol%.
  • the lower limit of this range may also be 0.01 mol% or 0.05 mol% or 0.1 mol% with increasing preference.
  • the associated upper limit may be 5 mol% or 2 mol% or 0.5 mol% for each of these lower limits with increasing preference.
  • the theoretical degree of crosslinking can be particularly preferably in a range from 0.1 to 2 mol% or even more preferably in a range from 0.01 to 0.5 mol%.
  • the degree of crosslinking in the sense of the invention is a quantitative measure for the characterization of polymeric networks. It is calculated, for example, as the quotient of the number of crosslinked basic building blocks and the number of moles of the basic building blocks present in this macromolecular network (monomer molecules). It is given either as a dimensionless number or as a percentage (mole fraction). Closely related to this (and often used as a synonym) is the concept of network density (here the number of networking sites is related to the volume).
  • the polymer foam according to the invention can preferably also not be melted without destruction. All relevant polymer foams from the prior art based on polystyrene are usually meltable, ie thermoplastic.
  • the polymer foam according to the invention is preferably also not soluble in a solvent.
  • its own monomer which makes up the polymer, is the best solvent for the polymer respective polymer.
  • the polymer foam according to the invention is not soluble in its own monomer.
  • the polymer foam preferably also contains a crosslinker.
  • the crosslinker preferably has at least 2 functional groups suitable for a polymerization reaction.
  • the functional groups are selected from vinyl, allyl, carboxylate, ethoxy, methoxy, amine, alcohol, ketone and allyl ketone groups.
  • the crosslinkers may be organically substituted silanes.
  • the crosslinker is particularly preferably selected from divinylbenzene, N, N-methylenebisacrylamide and ethylene glycol dimethacrylate.
  • the polymer foam also contains uncrosslinked polymer.
  • uncrosslinked polymer is understood as meaning a polymer which is formed by polymerization of monomer molecules (monofunctional, polymerizable molecule). It is microscopically in the form of uncrosslinked molecules.
  • the polymer foam preferably contains uncrosslinked polymer in a range from 2 to 90% by weight, more preferably from 10 to 75% by weight, very preferably from 30 to 60% by weight, based on the total weight of the polymer foam.
  • the polymer foam is open-celled.
  • the polymer foam is evacuable (e.g., under vacuum) without being destroyed.
  • the initial density of the foam (not the bulk density of the foam) is not significantly increased by the vacuum (shrinkage process ⁇ 30% by volume).
  • the sample is sealed in a plastic bag. production method
  • the object underlying the invention is achieved by a process for the preparation of the powder / particle according to the invention, in which at least the following steps are carried out: a) addition of crosslinker to monomer or a mixture of monomers to obtain a monomer mixture,
  • the swollen polymer is placed in a C0 2 atmosphere with a pressure in a range of 50 to 500 bar and a temperature in a range of 0 to 120 ° C,
  • the assembly can include grinding of the polymer foam.
  • the polymer foam may preferably be packaged in oil-permeable wraps (for example cushions, mats, sacks or hoses).
  • the specific surface of the foam material is even made optimally accessible at all, so that applications such as the above-mentioned application of the absorption of oil can only optimally result.
  • molded parts can also be produced.
  • step a) further additives can also be added in order to obtain the monomer mixture.
  • additives can be, for example, flame retardants, dyes, pigments, fillers, cleaning agents, water absorbers, powders / particles or mixtures thereof.
  • the polymer foam is ground with a mill, more preferably with an impingement jet mill. This is preferably cooled, more preferably cooled with liquid nitrogen.
  • the polymer Foaming is also preferably cooled before the grinding, more preferably cooled with liquid nitrogen.
  • the rotational speed of the mill is in a range of 100 to 14000 rpm.
  • the polymer foam is ground in several grinding operations, preferably in 1 to 5 grinding operations.
  • a clouding agent or a powder / particle can be added as step h) and intimately mixed with the powder / particle in order to obtain the composition according to the invention.
  • the addition of a further powder / particle can also be carried out in step g), provided that the further powder / particle survives a grinding process without damage.
  • the polymerization and foaming process take place spatially and temporally separated.
  • the swelling agent may be, for example, an organic solvent.
  • the monomer is preferably partially functionalized. Preferably, 0.001 to 1 mol% of all monomer molecules have an additional functional group compared to the other monomeric molecules. This may be, for example, a carboxylate group.
  • the pressure in step e) is in a range of 70 to 250 bar.
  • the temperature in step e) is from 30 to 90 ° C.
  • the monomer mixture also contains uncrosslinked polymer.
  • uncrosslinked polymer is also added in step a).
  • the opacifier is added after grinding to the polymer foam.
  • the monomer mixture is polymerized in step b) in water as a suspension. This is particularly advantageous because then spherical polymer granules are obtained.
  • the swelling agent is a ketone, more preferably acetone.
  • the swelling of the polymer is preferably carried out under normal conditions (1 bar (vapor pressure of the swelling agent at the given temperature, 20 ° C.) by immersing the polymer in the swelling agent.) Swelling preferably takes place in a range from 5 to 5,000 over a period of time The swelling process preferably takes place voluntarily and can be carried out already at room temperature and without additional input of energy
  • the polymer and the swelling agent can also be placed in a pressure-resistant container and the temperature increased an end, if no further swelling agent penetrates into the polymer. The swelling process thus reaches a plateau.
  • the object underlying the invention is achieved by a method for recovering the oil-binding agent, characterized in that the oil is expelled from the oil-binding agent.
  • the object underlying the invention is achieved by the use of the oil binder as a cleaning agent or cleaning agent additive (for example for textiles, woods, stones).
  • the oil may also be a phase change material.
  • phase change material for heat absorption and release.
  • phase change material laminate heat storage
  • the object underlying the invention is achieved by a composition comprising the inventive oil binder and an oil.
  • the oil may preferably be a phase change material (for example, an alkane such as n-tetradecane).
  • Fig. 1 nanofoam particles / granules with a diameter of 0.2 - 4 cm and a bulk density less than 500 kg / m 3 .
  • Fig. 5 Coarsely ground nanofoam powder in a scanning electron microscope with an intact nanostructure, magnification 50 times and a grain size of 20 to 1000 m ⁇ ti.
  • Fig. 6 Coarsely ground nanofoam powder in a scanning electron microscope with intact nanostructure, magnification 10,000 times
  • Fig. 7 Finely ground nanofoam powder in a scanning electron microscope with an intact nanostructure, 50x magnification and a particle size of 0.5 to 200 m ⁇ ti.
  • the concentration of the crosslinker is described by the mole fraction v of crosslinker and monomer. By an optional multiplication of the value by 100, the unit mol% is obtained.
  • the initiator initiating and maintaining the polymerization is described by the mole fraction s of initiator and monomer.
  • the IR opacifier is referred to as a mass fraction based on the total mass of components used and abbreviated to t.
  • the uncrosslinked polymer necessary to stabilize the opacifier particles is described by the mass fraction TT, the quotient of the mass of the uncrosslinked polymer and the total mass of components.
  • the polymerized polymer is converted into a dimensionally stable polymer gel before the foaming process.
  • the ratio of swelling agent and polymer is described by the mass fraction l.
  • a polystyrene foam is produced as described in WO 2015/071463A2 (cf., for example, FIG. 7, left foam).
  • This polystyrene foam had a pore size in the median of 100 nm.
  • the foam density was about 100 kg / m 3 .
  • the result was a nanofoam granules with a diameter of 0.2 - 4 cm and a bulk density of less than 500 kg / m 3 . This is shown in FIG. 1.
  • the nanofoam granules had a homogeneous nanostructure inside with a particle density of 30-300 kg / m 3 . This was then ground in a mill. Care was taken to ensure that the temperature of the nanofoam during the grinding process did not rise above the glass or melting temperature of the polymer.
  • the mill had to be permanently cooled. For this purpose, a collision current mill was particularly suitable, which was cooled with liquid nitrogen. Both the plant and the nanofoam granules to be ground were prepared in advance with liquid embroidery Fabric pre-cooled. Subsequently, the cooled nanofoam granulate was poured through an opening in the grinder.
  • the grinder could be operated with different rotational speeds, as well as gap widths between rotator and stator and thus allowed a variation of the particle sizes of the powder. Grain size distributions were always obtained.
  • the powder was collected at the exit of the plant. Subsequently, the powder was dried and could be further processed. The result can be seen in FIG. 2.
  • the milled powder showed a slightly lower bulk density than the bulk density of the granules used. This is related to the packing behavior of the grains.
  • the nanostructure of the individual grains remained during the grinding process. This was demonstrated by scanning electron micrographs FIGS. 3 to 8.
  • nanofoam can be mixed with any powders.
  • aggregates such as granules can be mixed or powder with granules.
  • the oil intake was determined according to LTwS-Nr. 27 (as of June 1999).
  • the person skilled in the art distinguishes between granules and powder in their different size ranges of the individual particles or particles. Both terms summarize an accumulation of several particles or particles.
  • a granule has larger particles than a powder.
  • the particles have a spherical shape and can thus ideally be geometrically described with a diameter. Since, in particular, no geometric shape can be assumed for powder particles (see FIGS. 5, 7 and 8), it makes more sense to speak of a particle size.
  • the particle size denotes the largest possible distance, which is possible by a straight line in the particle. This can also be determined in practice by a sieving process.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un liant de pétrole contenant des particules (poudre/granulat) composées de mousse, un procédé de fabrication dudit liant de pétrole ainsi qu'un procédé pour lier du pétrole, un procédé de récupération du liant de pétrole, l'utilisation du liant de pétrole dans un produit de nettoyage et une composition contenant ledit liant de pétrole et du pétrole.
PCT/EP2019/053662 2018-02-15 2019-02-14 Liant de pétrole WO2019158642A1 (fr)

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EP19706461.1A EP3752571A1 (fr) 2018-02-15 2019-02-14 Liant de pétrole

Applications Claiming Priority (2)

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DE102018103457.1A DE102018103457A1 (de) 2018-02-15 2018-02-15 Ölbindemittel
DE102018103457.1 2018-02-15

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WO2019158642A1 true WO2019158642A1 (fr) 2019-08-22

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EP (1) EP3752571A1 (fr)
DE (1) DE102018103457A1 (fr)
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US4636527A (en) 1985-04-12 1987-01-13 The Dow Chemical Company Method for the preparation of styrene polymer foam and foam prepared thereby
WO1993022371A1 (fr) 1992-04-24 1993-11-11 The Dow Chemical Company Mousse de polystyrene et son procede de fabrication
EP0849309B1 (fr) 1996-12-18 2000-03-08 SIRAP-GEMA S.p.A. Méthode de production d'une feuille en polystyrène expansé à cellules ouvertes et barquette d'emballage
US20050047980A1 (en) * 2003-08-29 2005-03-03 Hiroshi Sakaguchi Solidifying material for a liquid organic compound, use thereof, and method of solidifying an organic compound
DE10358800A1 (de) 2003-12-12 2005-07-14 Basf Ag Expandierbare Styrolpolymergranulate
AT501328B1 (de) 2005-01-18 2007-02-15 Abwasserreinigung Region Dornb Ölbindemittel
AT508590B1 (de) 2009-07-31 2011-07-15 Zwittnig Leopold Ölbindemittel
DE102010022437B4 (de) 2010-04-13 2012-11-29 Wachs-Chemie Elsteraue E.K. Ölbindemittel und Bindemittel für Lösemittel, deren Herstellung sowie deren Verwendung
DE202013003522U1 (de) 2013-04-13 2013-05-16 Georg-Ernst Graetzer ÖL-EX Ölbindemittel
CH707445A2 (de) 2013-01-14 2014-07-15 Anton Schmalz Ölbindemittel aus Baumrinde zum Aufnehmen von Öl.
DE102013223391A1 (de) 2013-11-15 2015-05-21 Universität Zu Köln Herstellung von porösen Materialien durch Expansion von Polymergelen
WO2016081992A1 (fr) * 2014-11-25 2016-06-02 Deakin University Matériau absorbant
WO2017021436A1 (fr) * 2015-08-05 2017-02-09 Tesa Se Mousse émulsionnée microcellulaire

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DE2635087A1 (de) 1976-08-04 1978-02-09 Bayer Ag Oelbindemittel
US4636527A (en) 1985-04-12 1987-01-13 The Dow Chemical Company Method for the preparation of styrene polymer foam and foam prepared thereby
WO1993022371A1 (fr) 1992-04-24 1993-11-11 The Dow Chemical Company Mousse de polystyrene et son procede de fabrication
EP0849309B1 (fr) 1996-12-18 2000-03-08 SIRAP-GEMA S.p.A. Méthode de production d'une feuille en polystyrène expansé à cellules ouvertes et barquette d'emballage
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DE10358800A1 (de) 2003-12-12 2005-07-14 Basf Ag Expandierbare Styrolpolymergranulate
AT501328B1 (de) 2005-01-18 2007-02-15 Abwasserreinigung Region Dornb Ölbindemittel
AT508590B1 (de) 2009-07-31 2011-07-15 Zwittnig Leopold Ölbindemittel
DE102010022437B4 (de) 2010-04-13 2012-11-29 Wachs-Chemie Elsteraue E.K. Ölbindemittel und Bindemittel für Lösemittel, deren Herstellung sowie deren Verwendung
CH707445A2 (de) 2013-01-14 2014-07-15 Anton Schmalz Ölbindemittel aus Baumrinde zum Aufnehmen von Öl.
DE202013003522U1 (de) 2013-04-13 2013-05-16 Georg-Ernst Graetzer ÖL-EX Ölbindemittel
DE102013223391A1 (de) 2013-11-15 2015-05-21 Universität Zu Köln Herstellung von porösen Materialien durch Expansion von Polymergelen
WO2015071463A2 (fr) 2013-11-15 2015-05-21 Universität Zu Köln Préparation de matériaux poreux par expansion de gels polymères
WO2016081992A1 (fr) * 2014-11-25 2016-06-02 Deakin University Matériau absorbant
WO2017021436A1 (fr) * 2015-08-05 2017-02-09 Tesa Se Mousse émulsionnée microcellulaire

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OKOLIEOCHA C.; RAPS D.; SUBRAMANIAM K.; ALTSTÄDT V., EUROPEAN POLYMER JOURNAL, vol. 73, 2015, pages 500 - 519

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