EP2355656A2 - Verfahren zur herstellung von insektizid ausgerüsteten xps-formteilen - Google Patents
Verfahren zur herstellung von insektizid ausgerüsteten xps-formteilenInfo
- Publication number
- EP2355656A2 EP2355656A2 EP09744660A EP09744660A EP2355656A2 EP 2355656 A2 EP2355656 A2 EP 2355656A2 EP 09744660 A EP09744660 A EP 09744660A EP 09744660 A EP09744660 A EP 09744660A EP 2355656 A2 EP2355656 A2 EP 2355656A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- insecticide
- xps
- polymer melt
- butyl
- melt
- 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- Withdrawn
Links
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/16—Foams
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
Definitions
- the invention relates to a process for the preparation of insecticidal foam molded parts made of extruded polystyrene foam (XPS moldings), obtainable by the process insecticidal XPS moldings and their use in construction.
- XPS moldings extruded polystyrene foam
- Polymer foams and foam moldings are e.g. used in the construction industry as insulation material underground and above ground. Insects, especially termites, can substantially damage such foams by feeding, so that the insulating effect and the mechanical stability of the shaped bodies are restricted and a further penetration of the pests is made possible. In many cases, even legal regulations prescribe an insecticidal protection of moldings, since such insulation materials offer a preferred habitat for termites.
- J P-2000-001564 describes the use of ( ⁇ ) -5-amino-1- (2,6-dichloro- ⁇ , ⁇ , ⁇ , -trifluoro-p-tolyl) -4-trifluoromethylsulfinylpyrazole (Common Name: Fipronil ) for the protection of polymer foams. Fipronil is used in concentrations of 0.001-1 wt .-%. Polystyrene, polyethylene and polypropylene are described as polymer matrix. The incorporation of fipronil by applying to the surface of the prefoamed foam particles or by applying to the propellant containing granules. JP 2001-259271 describes a process in which propellant-containing EPS granules or prefoamed EPS granules are coated with fipronil and a binder.
- WO 00/44224 discloses the production of insecticidal foam boards by extruding or pressing an expandable polymer composition containing a pyrethroids insecticide dispersed therein.
- the process described relates to the production of XPS (extruded polystyrene foam).
- the active ingredients used are structurally significantly different from the active compounds according to the invention.
- the insecticidal activity of the foams described there to insects is also unsatisfactory.
- the object of the invention is to remedy the aforementioned disadvantages and to provide an economical process for the production of XPS molded parts with sustainable and improved insecticidal effectiveness. It has been found that insecticidal active compounds according to the invention can be incorporated homogeneously into a polymer melt without decomposition.
- the invention thus provides a process for preparing insecticidal extruded polystyrene foam (XPS) molded parts comprising the steps
- step (a) and / or (b) at least one insecticide from the group of phenylpyrazoles, chlorfenapyr and hydramethylnone is introduced into the polymer melt.
- the invention furthermore relates to XPS molded parts obtainable by the process according to the invention and to their use as construction material, in particular as insulation material, in construction.
- the insecticide is particularly firmly and uniformly incorporated into the polymer matrix. This reduces the loss of active ingredient and exposure to the insecticide during the manufacture, processing and use of XPS molded parts. In addition, a reduction of the necessary amount of insecticide is possible by the method according to the invention.
- insecticide-treated XPS moldings according to the invention have no disadvantages in mechanical and insulating properties compared to a standard product (without insecticide).
- polystyrene is used as a collective term for homopolymers and copolymers of styrene, other vinylaromatic monomers and, if desired, further comonomers.
- PS are, for example, standard polystyrene (general purpose polystyrene, GPPS, usually crystal clear), impact polystyrene (high impact polystyrene, HIPS containing, for example, polybutadiene or polyisoprene rubber), styrene-maleic acid (anhydride) polymers, Acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile polymers (SAN), ⁇ -methylstyrene-acrylonitrile polymer (AMSAN), or mixtures thereof, to be understood (component K1).
- ABS Acrylonitrile-butadiene-styrene polymers
- SAN styrene-acrylonitrile polymers
- AMSAN
- Preferred PS is standard polystyrene, ie a polystyrene with a molar styrene moiety. a minimum of 95% Further preferred PS is ⁇ -methylstyrene-acrylonitrile polymer (AMSAN).
- AMSAN ⁇ -methylstyrene-acrylonitrile polymer
- PS also comprises blends of one or more of the abovementioned polymers (component K1) with one or more thermoplastic polymers (component K2), for example polyphenylene ethers (PPE), polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethylmethacrylate (PMMA), polycarbonates (PC), polyesters, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulphones (PES), polyetherketones (PEK) or polyethersulphides (PES).
- PPE polyphenylene ethers
- PA polyamides
- PA polyolefins
- PP polypropylene
- PE polyethylene
- PMMA polymethylmethacrylate
- PC polycarbonates
- polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulphones (PES
- the polymers of component K1 mentioned are obtainable by polymerization of one or more vinylaromatic monomers, such as styrene, and if desired further comonomers, such as dienes, ⁇ , ⁇ -unsaturated carboxylic acids, esters (preferably alkyl esters) or amides of these carboxylic acids and alkenes. Suitable polymerization methods are known to the person skilled in the art.
- At least one compound of the general formula (I) is chosen as the vinylaromatic monomer
- R 1 and R 2 are each independently hydrogen, methyl or ethyl
- R 3 is hydrogen, Ci-Ci O -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec-pentyl, neo-pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl; preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; and
- k stands for an integer from 0 to 2.
- Styrene is particularly preferred;
- ⁇ -methylstyrene, p-methylstyrene, ethylstyrene, rol, tert-butylstyrene, vinylstyrene, ⁇ -vinyltoluene, 1, 2-diphenylethylene, 1, 1-diphenylethylene or mixtures thereof are particularly suitable.
- Suitable diene comonomers are all polymerizable dienes, in particular 1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 2,3-dimethylbutadiene, isoprene, piperylene or mixtures thereof. Preference is given to 1,3-butadiene (in short: butadiene), isoprene or mixtures thereof.
- ß-unsaturated carboxylic acid or its derivatives are preferably compounds of general formula (II),
- R 5 is selected from the group consisting of
- Ci-Ci o alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl ; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- R 4 is selected from the group consisting of
- Ci-Ci o alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec Pentyl, neo-pentyl, 1,2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably hydrogen;
- R 6 is selected from the group consisting of Hydrogen (with which compound (II) is the carboxylic acid itself), or unbranched or branched C 1 -C 10 -alkyl (with which compound II is a carboxylic acid ester), such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl , n-hepyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, e
- Preferred compounds of the formula (II) are acrylic acid and methacrylic acid. Further preferred are the back CrCio-alkyl esters of acrylic acid, in particular the butyl, preferably n-butyl acrylate, and the Ci-Ci o alkyl ester of methacrylic acid, particularly methyl methacrylate (MMA).
- MMA methyl methacrylate
- carboxylic acid amides are the amides of the abovementioned compounds (II), for example acrylamide and methacrylamide.
- R 8 is selected from the group consisting of
- C 1 -C 10 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
- neo-pentyl 1,2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; or hydrogen;
- R 7 is selected from the group consisting of unbranched or branched Ci-Cio-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2 Ethylhexyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, is
- R 9 is selected
- Ci-Ci o alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec Pentyl, neo-pentyl, 1,2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
- X is selected from the group consisting of - hydrogen, - glycidyl
- Groups with tertiary amino groups preferably NH (CH 2 ) bN (CH 3 ) 2 , where b is an integer in the range of 2 to 6, enolisable groups having 1 to 20 C-atoms, preferably acetoacetyl, of the formula
- R 10 is selected from straight-chain or branched C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- Nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl
- R 8 in formula (IIIa) or (INb) is selected from hydrogen and methyl and R 7 and R 9 are each hydrogen.
- the compound of the formula (Va) is methylolacrylamide.
- the PS can also be prepared using alkenes as comonomers.
- alkenes are ethylene (ethene) and propylene (propene).
- suitable comonomers for the preparation of component K1 are, for example, in each case 1 to 5% by weight of (meth) acrylonitrile, (meth) acrylamide, ureido (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Acrylamidopropansulfonkla- re (branched or unbranched) or the sodium salt of vinylsulfonic acid.
- polystyrenes (PS) which can be used according to the invention can be prepared by processes known to those skilled in the art, for example by free-radical, anionic or cationic polymerization, in bulk, solution, dispersion or emulsion. Preference is given to free-radical polymerization.
- the polystyrenes which can be used in the process according to the invention generally have weight-average molecular weights of 100,000 to 300,000 g / mol and a melt volume rate MVR (200 ° C./5 kg) to ISO 113 in the range from 1 to 10 cm 3 .
- Suitable polystyrenes are, for example, PS 158 K, 168 N or 148 G from BASF SE.
- step (a) of the process of the invention the polystyrene is heated to obtain a polymer melt.
- the formation of a polymer melt is understood to mean a plasticization of the polystyrene in a broader sense, ie the conversion of the solid polystyrene into a deformable or flowable state.
- a temperature above the melting or glass transition temperature Suitable temperatures are generally from 50 to 250 0 C, preferably 100 to 220 0 C, particularly preferably 180 to 220 0 C.
- a polystyrene used in a molar styrene monomer content of 95% it must be heated to a temperature of at least 180 0 C. to obtain a polymer melt.
- step (a) of the process according to the invention can be carried out by means of any means known in the art, such as by means of an extruder, mixer (eg kneader). Preference is given to the use of Aufschmelzextrudern (primary extruders).
- Step (a) of the process according to the invention can be carried out continuously or batchwise, a continuous process being preferred.
- Step (b) of the process according to the invention comprises introducing a blowing agent into the polystyrene melted in step (a) to form a foamable melt.
- the propellant may be incorporated into the molten polystyrene by any method known to those skilled in the art. Suitable examples are extruders or mixers (eg kneader).
- the blowing agent is mixed with the molten polystyrene under elevated pressure.
- the pressure must be high enough to substantially prevent the molten polymer material from foaming and to achieve a homogeneous distribution of the blowing agent in the molten polystyrene. Suitable pressures are 50 to 500 bar (absolute), preferably 100 to 200 bar (absolute), more preferably 120 to 170 bar (absolute).
- the temperature in step (b) of the process according to the invention must be selected such that the polymeric material is in the molten state.
- step (b) of the process according to the invention is generally carried out at temperatures of 100 to 280 0 C, preferably 120 to 260 0 C, and particularly preferably 180 to 220 0 C.
- Step (b) may be carried out continuously or batchwise, preferably step (b) is carried out continuously.
- the blowing agent can be added in the melt extruder (primary extruder) or in a downstream step.
- the foamable polymer melt is prepared in XPS extruders known to the person skilled in the art, for example via a tandem structure consisting of a melting extruder (primary extruder) and a cooling extruder (secondary extruder).
- the process can be carried out continuously or batchwise, wherein the polystyrene is melted in the primary extruder (step (a)) and the addition of the blowing agent (step (b)) to form a foamable melt also takes place in the primary extruder.
- the blowing agent provided with melt in Sekudärextruder to a suitable temperature for foaming of 50-180 0 C, preferably to a temperature of 80-130 0 C, cooled.
- Suitable propellants include inorganic, organic and chemically reactive propellants.
- Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air and helium.
- a preferred blowing agent is a mixture of carbon dioxide and water.
- Organic propellants include aliphatic hydrocarbons having 1 to 9 carbon atoms and per- or partially-halogenated aliphatic hydrocarbons having 1 to 4 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, iso-butene, n-pentane, iso-pentane, and neopentane.
- Fully and partially halogenated aliphatic hydrocarbons include fluorocarbon compounds, chlorocarbon compounds and chlorofluorocarbon compounds.
- fluorocarbon compounds include methyl fluoride, perfluoromethane, ethyl fluoride, difluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1, 1, 1-trifluoropropane, perfluoropropane, difluoropropane, difluoropropane, perfluorobutane, perfluorocyclopentane.
- Partially halogenated chlorocarbon compounds and chlorofluorocarbon compounds which are suitable for use in the process according to the invention include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, chlorodifluoromethane, 1,1-dichloro-1-fluoroethane, 1-chloro -1, 1-difluoroethane, 1, 1-dichloro-2,2,2-trifluoroethane and 1-chloro-1, 2,2,2-tetrafluoroethane.
- Fully halogenated chlorofluorohydrocarbon compounds include trichloromonofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, 1,1,1-trifluoroethane, pentafluoroethane,
- Chemically reactive blowing agents include azodicarboxylic acid diamide, azodiisobutyronitrile, benzoylsulfonate, 4,4-oxibenzenesulfonylsemicarbazide, p-
- Another preferred blowing agent mixture comprises 0 to 100% by weight of carbon dioxide, 0 to 50% by weight of water and 0 to 75% by weight of an alcohol, for example methanol or ethanol, of a ketone or ether.
- inorganic propellants For environmental reasons, it is desirable to use inorganic propellants, if possible.
- Two particularly suitable inorganic blowing agents are carbon dioxide and water.
- the amount of blowing agent used is 0.5 to 20 wt .-%, preferably 4 to 12 wt .-%, and in particular 2 to 8 wt .-%, based on the polystyrene used.
- nucleating agent is added to the molten polymeric material.
- Nucleating agents may be finely divided, inorganic solids such as talc, metal oxides, silicates or polyethylene waxes in amounts of generally from 0.1 to 10% by weight, preferably from 0.1 to 3% by weight, more preferably from 1 to 1.5 % By weight, based on the polymeric material. be set.
- the average particle diameter of the nucleating agent is generally in the range of 0.01 to 100 .mu.m, preferably 1 to 60 microns.
- a particularly preferred nucleating agent is talc, for example talc from Luzenac Pharma.
- the nucleating agent can be added to the polymer melt by methods known to those skilled in the art. The addition can be carried out in step (a) and / or (b).
- additives such as nucleating agents, plasticizers, flame retardants, IR absorbers such as carbon black or graphite, aluminum powder and titanium dioxide, soluble and insoluble dyes and pigments can be added in step (a) and / or (b).
- Preferred additives are graphite and carbon black.
- graphite is added in amounts of generally 0.05 to 25% by weight, more preferably in amounts of 2 to 8% by weight, based on the polymeric material.
- Suitable particle sizes for the graphite used are in the range from 1 to 50 ⁇ m, preferably in the range from 2 to 10 ⁇ m.
- the XPS molding of the invention may be inked to allow easy discrimination against non-insecticidal XPS moldings and thus increase product safety.
- one or more flame retardants are added in step (a) and / or (b).
- Suitable flame retardants are, for example, tetrabromobisphenol A diallyl ether, expandable graphite, red phosphorus, triphenyl phosphate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
- Another suitable flame retardant is, for example, hexabromocyclododecane (HBCD), in particular the industrial products which essentially contain the ⁇ -, ⁇ - and ⁇ -isomer and preferably an addition of dicumyl peroxide as synergist.
- HBCD hexabromocyclododecane
- At least one insecticide from the group of the phenylpyrazoles, in particular fipronil (IV), acetoproles, ethiproles (V) and the compound of the formula (VI), chlorfenapyr (VII) and hydramethylnone (VIII) is mixed into the polymer melt used.
- the interference can be carried out in steps a) and / or b).
- the at least one insecticide is not critical, so the at least one insecticide can be carried out as a pure substance, as a formulation or in the form of a masterbatch. It is also possible in step a) to use a PS which already contains at least one insecticide.
- pure substance is understood as meaning substances which have an active ingredient content of at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight and particularly preferably at least 97% by weight, in each case on the total weight of the pure substances.
- formulations are meant all known insecticidal formulations known to those skilled in the art.
- the use of commercially available formulations is also possible. Preference is given to the use of aqueous formulations.
- Masterbatches are understood to mean PS that contain at least one insecticide at a higher concentration than the final concentration. End concentration is understood to mean the concentration of the at least one insecticide in the XPS molded part. Suitable insecticide concentrations for a masterbatch are in the range of 1 to 90% by weight. Preferably, the masterbatch contains less than 20 wt .-%, more preferably 1 to 15 wt .-% and in particular 5 to 10 wt .-% of the at least one insecticide, each based on the total weight of the masterbatch.
- Suitable methods for masterbatch production are, for example, the incorporation of the at least one insecticide in an extruder into a polymer melt or the coating of PS with an insecticide or an insecticide mixture.
- Suitable mixing ratios of the masterbatch and of the commercial PS used in the process according to the invention are in the range from 10: 1 to 1: 1000, more preferably in the range from 10: 1 to 1: 100 and in particular in the range from 10: 1 to 1:50.
- the at least one insecticide in step (a) and / or (b) is added as a pure substance.
- the addition of the at least one insecticide in step (a) and / or (b) takes place in the form of an aqueous formulation.
- the at least one insecticide is incorporated into a polymer melt in an extruder at a higher than the final concentration (masterbatch preparation) and then this active substance-containing polymer in step (a) and / or (b) is fed to the polymer melt.
- the feed can be effected, for example, by mixing into the main stream of the polymers, shortly after melting, or via a side stream which serves to introduce additives into the main stream.
- the batch preparation is carried out by coating a PS with an insecticide or an insecticide mixture.
- PS granules are used for this purpose. The coating is carried out by known, familiar to the expert methods.
- the insecticide or the insecticide mixture can be used solid, dissolved and / or dispersed (for example suspended or emulsified).
- the insecticide or the insecticide mixture is applied to the PS to be coated, for example, by spraying or tumbling in conventional mixers. It is also possible to immerse or wet the PS in a suitable solution, dispersion, emulsion or suspension. If desired, further coating additives such as binders, antistatics, water repellents, flame retardants, finely divided silica and inorganic fillers may be added to the insecticide or insecticide mixture.
- the coated PS obtained in this way is, in one embodiment, together with commercial uncoated PS according to known methods known to the person skilled in the art, e.g. melted in an extruder and processed by the process according to the invention to XPS moldings.
- the addition of the coated PS to the commercially available uncoated PS preferably takes place in step (a) of the process according to the invention. It is also possible to mix the coated and the commercial uncoated PS in an upstream step and then to supply step (a).
- the at least one insecticide in step (a) is added as pure substance.
- the at least one insecticide in step (a) is added in the form of a formulation.
- the at least one insecticide in step (a) is added in the form of an aqueous formulation.
- step (a) and / or (b) The amount of addition of the at least one insecticide in step (a) and / or (b) is arbitrary, but is preferably chosen so that the XPS invention
- Suitable insecticides are phenylpyrazoles, in particular fipronil (( ⁇ ) -5-amino-1- (2,6-dichloro- ⁇ , ⁇ , ⁇ , -trifluoro-p-tolyl) -4-trifluoromethylsulfinylpyrazole), hydramethylnon and chlorfenapyr ,
- fipronil is preferably fipronil.
- biocides or fungicides may be added (in mixture).
- Suitable mixing partners are, for example, from the group of insecticides:
- Organo (thio) phosphates acephates, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoates, disulphoton, ethion, fenitrothion, fenthion, isofenphos, isoxathione, malathion, methamidophos, methidathion, Methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone, pharate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorovinphos, terbufos, triazophos, trichlorfon;
- Pyrethroids allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profuthrin, dimermuthrin;
- Growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorofluorotron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, sulfluramide, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) Ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide, Azadirachtin; c) Juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- Nicotine receptor agonists / antagonists acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam;
- GABA antagonists endosulfan, pyrafluprole, pyriprole;
- Macrocyclic lactone insecticides abamectin, emamectin, milbemectin, lepimetin, spinosad;
- Site I electron transport inhibitors for example, fenazaquin, fenpyroximate pyrimidifen, pyridaben, tebufenpyrad, tofenphenyl, flufenerim, hydramethylnone, dicofol;
- Inhibitors of chitin biosynthesis cyromazine
- Lepimectin is known from "Agro Project”, PJB Publications Ltd, November 2004. Benclothiaz and its preparation is described in EP-A1 454621. Methidathione and paraoxon and their preparation are described in “Farm Chemicals Handbook”, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation is described in WO 98/28277. Flupyrazofos is described in "Pesticide Science” 54, 1988, pages 237-243 and in US 4822779.
- Pyrafluproles and its preparation are described in JP 2002193709 and in WO 01/00614 Pyriprole and its preparation are described in WO 98/45274 and in US Pat Amidoflumet and its preparation are described in US 6221890 and in JP 21010907. Flufenerim and its manufacturer ment is described in WO 03/007717 and in WO 03/007718. Cyflumetofen and its preparation is described in WO 04/080180.
- W is Cl or CF 3 ;
- X, Y are the same or different Cl or Br;
- R 11 is (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -alkenyl, (C 3 -C 6 ) -alkynyl or (C 3 -C 6 ) -
- Cycloalkyl which may be substituted by 1 to 3 halogen atoms, or the (C 2 -C 4 ) -alky I substituted by (dC 4 ) -alkoxy;
- R 12 , R 13 are (C 1 -C 6 ) -alkyl or, together with the carbon atom to which they are attached, form (C 3 -C 6 ) -cycloalkyl which may be substituted by 1 to 3 halogen atoms;
- R 14 is H or (C r C 6 ) alkyl, as well as enantiomers and salts thereof.
- R 11 is preferably (C 1 -C 4 ) -alkyl, especially methyl or ethyl;
- R 12 and R 13 are preferably methyl or form, with the carbon atom to which they are attached, a cyclopropyl ring which can carry one or two chlorine atoms;
- R 14 is preferably (C 1 -C 4 ) -alkyl, in particular methyl;
- W is preferably CF 3 ;
- X, Y are preferably Cl.
- Further preferred compounds of the formula (IX) are those in which X and Y are Cl, W is CF 3 , R 12 , R 13 and R 14 are methyl and R 11 is methyl or ethyl, as well as those compounds in which X, Y Cl , W CF 3 , R 12 , R 13 together with the carbon atom to which they are attached form a 2,2-dichlorocyclopropyl group, R 14 is methyl and R 11 is methyl or ethyl.
- These compounds and their preparation are described for example in US 2007/0184983.
- pyrethroids 1.3
- neonicotin receptor agonists / antagonists 1.5
- borates carbaryl
- chlorantraniliproles chlorpyrifos
- diflubenzuronum fenitrothion
- flonicamid flufenoxuron
- flonicamid flufenoxuron
- indoxacarb indoxacarb are preferred as mixing partners , Isofenphos, Noviflumuron, Metaflumizone, Spinosad, Sulfluramid.
- acetamidol bifentrhin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, deltamethrin, fenvalerate, imidacloprid, lambda-cyhalothrin, permethrin, thiacloprid and thiamethoxam.
- fipronil with one or more of the said mixture partners, in particular fipronil with ⁇ -cypermethrin and / or peronyl butoxide (PBO). Also particularly preferred is the use of fipronil without a further mixing partner.
- PBO peronyl butoxide
- the mixing ratio between the insecticides used according to the invention and optionally other mixing partners can vary within wide limits and is generally 0.1: 100 to 100: 0.1.
- the insecticide or the insecticide mixture can be used as a pure substance (for example as a technical or pure active ingredient).
- the use of commercially available formulations is also possible.
- the addition amount of the insecticide or insecticide mixture to the polymer melt is selected such that the XPS moldings obtainable therefrom have concentrations of from 10 to 1000 ppm, more preferably from 20 to 1000 ppm and most preferably from 50 to 500 ppm.
- Step (c) of the process of the invention comprises foaming the foamable melt to obtain an XPS molded article.
- the melt is conveyed through a suitable device, for example a nozzle plate.
- the nozzle plate is heated at least to the temperature of the blowing agent-containing polymer melt.
- the temperature of the nozzle plate is preferably from 50 to 200 ° C. More preferably, the temperature of the nozzle plate is from 100 to 150 ° C.
- the propellant-containing polymer melt is transferred through the nozzle plate into a region in which a lower pressure prevails than in the region in which the foamable melt is held prior to extrusion through the die plate.
- the lower pressure may be superatmospheric or subatmospheric.
- the extrusion is in a region of atmospheric pressure.
- Step (c) is also carried out at a temperature at which the to be foamed polymeric material is in the molten state, generally at temperatures from 50 to 150 0 C, preferably at 100 to 125 0 C.
- a temperature at which the to be foamed polymeric material is in the molten state generally at temperatures from 50 to 150 0 C, preferably at 100 to 125 0 C.
- the XPS moldings obtainable by the process according to the invention preferably have a rectangular cross-section.
- the thickness of the XPS molding is determined by the height of the nozzle plate slot.
- the width of the XPS molding is determined by the width of the nozzle plate slot.
- the length of the molding is determined in a subsequent operation by known to those skilled methods such as bonding, welding, sawing and cutting.
- Particularly preferred are XPS molded parts with a plate-shaped geometry (XPS plates). Plate-shaped means that the dimension of the thickness (height) is small in comparison with the dimension of the width and the dimension of the length of the molding.
- the XPS molded parts according to the invention generally have a compressive strength, measured in accordance with DIN EN 826, in the range from 0.3 to 1.0 N / mm 2 , preferably in the range from 0.35 to 0.7 N / mm 2 , Preferably, the density of the foam sheets is in the range of 25 to 50 kg / m 3 .
- the XPS plates according to the invention preferably have cells which, measured according to DIN ISO 4590, are at least 90%, in particular 95 to 100%, closed-cell.
- the insecticide or the insecticide mixture is distributed in a molecularly dispersed manner in the XPS moldings according to the invention.
- molecular dispersant means that the active ingredient in the polymer matrix is so finely distributed that no crystalline fractions of the active ingredient can be detected by X-ray diffractometry. Such a condition is also called a "fixed solution”.
- the term "no crystalline fractions" means that less than 3% by weight of crystalline fractions are present Differential Scanning Calorimetry (DSC) In the case of a molecular dispersion, no melting peak is observed in the area of the melting point of the active substance.
- the detection limit of this method is 1% by weight.
- Solid solutions lead to an improved release of the active ingredient.
- An important requirement for solid solutions is that they are stable even when stored for a long time, i. h., That the active ingredient does not crystallize.
- the capacitance of the solid solution in other words the ability to form stable solid solutions with as high an active substance content as possible, is also important.
- the invention also relates to the use of the XPS molded parts according to the invention.
- the XPS molded parts according to the invention in the construction industry, for example as insulation material above and below ground to avoid or reduce the damage of these molded parts by pests, such as insects, which can cause substantial damage to the molded parts by eating so that the insulating effect and the mechanical stability of the molded parts are restricted and a further penetration of the pests is made possible.
- the moldings produced according to the invention are particularly suitable for preventing or reducing the damage caused by termites. The invention is explained in more detail by the examples, without being limited thereto.
- a fipronil-coated PS granulate is used as the source of fipronil (product from Example 1) which is metered in and mixed with the other components in the respective mixing ratios.
- the extrusion temperature is a maximum of 200 0 C.
- Foamed is a 22 mm wide slit die at a rate of 7 kg / h. Comparative Example:
- deltamethrin active substance formulation (Decis Micro (deltamethrin 62.5 g ai / kg, Bayer Crop Science) were mixed in 100 ml of water and the mixture was introduced into an Alexanderwerk stirrer with 6150 g of polystyrene (PS 158k, BASF SE) and mixed. The mixture was dried overnight.
- thermocycling (deltamethrin) -containing foams on the extruder
- the deltamethrin-coated PS granulate (product from 3) serves as source of delta-methrin, which is metered in and mixed with the other components in the respective mixing ratios.
- the extrusion temperature is a maximum of 200 0 C. Foamed is a 22mm wide slot die at a rate of 7 kg / h.
- the biological test method was similar to the biological experiment method of Su et al. (1993) for determining the effect of soil miticides. Cylinders (approximately 2.5 cm in diameter and 5.0 cm in length) were cut from blocks using a pincushion drill. Each Polystyrolzylin- was wedged into a 2.5 cm by measuring Tenite ® -Polyesterrschreibchen. This tube was then connected via a Tygon connection tube to another tube containing 80 workers and a soldier. The 5.0 cm polystyrene cylinders were inserted between two 3 cm agar segments. Yellow pine and paper strip shavings served as feed and nest for termites in both the termite tube and the polystyrene cylinder tube. The tubes were held at 25 ° C. during the seven-day experimental period.
- the route tunneled through the outer surface of the cylinder along the inner wall of the tube was recorded every 24 hours. Short ( ⁇ 10mm) straight tunnels on the outside of the cylinder were measured with a ruler. Longer, curved tunnels were measured by placing a section of rubber band along the course of the tunnel and then measuring the length of the rubber band. The trial ended after seven days. At the time of termination, mortality and the length of the tunnel tunnelled through the interior of the cylinder were determined by threading small pieces of 0.5 mm insulated telephone wire through the tunnels and, after pulling out the wire, determining its length with a ruler.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Building Environments (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP09744660A EP2355656A2 (de) | 2008-10-22 | 2009-10-21 | Verfahren zur herstellung von insektizid ausgerüsteten xps-formteilen |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP08167227 | 2008-10-22 | ||
PCT/EP2009/063780 WO2010046379A2 (de) | 2008-10-22 | 2009-10-21 | Verfahren zur herstellung von insektizid ausgerüsteten xps-formteilen |
EP09744660A EP2355656A2 (de) | 2008-10-22 | 2009-10-21 | Verfahren zur herstellung von insektizid ausgerüsteten xps-formteilen |
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EP2355656A2 true EP2355656A2 (de) | 2011-08-17 |
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EP09744660A Withdrawn EP2355656A2 (de) | 2008-10-22 | 2009-10-21 | Verfahren zur herstellung von insektizid ausgerüsteten xps-formteilen |
Country Status (10)
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US (1) | US20110201662A1 (de) |
EP (1) | EP2355656A2 (de) |
JP (1) | JP2012506403A (de) |
KR (1) | KR20110080169A (de) |
CN (1) | CN102256483A (de) |
AU (1) | AU2009306466A1 (de) |
BR (1) | BRPI0919713A2 (de) |
MX (1) | MX2011004119A (de) |
TW (1) | TW201019853A (de) |
WO (1) | WO2010046379A2 (de) |
Families Citing this family (3)
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EP2580961A1 (de) | 2011-10-11 | 2013-04-17 | LANXESS Deutschland GmbH | Mischungen aus treibmittelhaltigen Polymeren, Insektiziden und Wachsen |
CN109306069A (zh) | 2013-03-15 | 2019-02-05 | 欧文斯科宁知识产权资产有限公司 | 在使用低全球变暖的潜在发泡剂制造挤出聚苯乙烯泡沫体中使用的加工助剂 |
AT516041B1 (de) * | 2014-08-26 | 2016-02-15 | Ifn Holding Ag | Fenster |
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US2927040A (en) * | 1957-08-13 | 1960-03-01 | Davis Chester | Non-staining triarylmethane color base and method of printing therewith |
BE785883A (fr) * | 1971-07-05 | 1973-01-05 | Hoechst Ag | Particules transformables en mousse a base de polymeres du styrene |
KR900003088B1 (ko) * | 1988-03-26 | 1990-05-07 | 재단법인 한국화학연구소 | 5-하이드록시피라졸 유도체 |
US5169951A (en) * | 1990-04-23 | 1992-12-08 | Ciba-Geigy Corporation | Process for preparing nematicidal compositions |
FR2714685B1 (fr) * | 1994-01-05 | 1996-08-02 | Cecil | Procédé pour la protection antitermite des constructions. |
WO1998045274A1 (fr) * | 1997-04-07 | 1998-10-15 | Mitsubishi Chemical Corporation | Derives de pyrazole, leur procede de preparation, intermediaires et pesticide comprenant ces derives comme composant actif |
WO1999041983A1 (en) * | 1998-02-20 | 1999-08-26 | Battelle Memorial Institute | Barrier preventing wood pest access to wooden structures |
JP2000001564A (ja) * | 1998-06-18 | 2000-01-07 | Nippon Nohyaku Co Ltd | 防蟻性樹脂発泡成型体 |
US6156328A (en) * | 1999-02-01 | 2000-12-05 | The Dow Chemical Company | Insecticide-containing foam sheet and process for the preparation thereof |
KR100784746B1 (ko) * | 1999-06-29 | 2007-12-13 | 니혼노야쿠가부시키가이샤 | 피라졸 유도체 및 그 제조방법, 그리고 이를 유효성분으로하는 유해생물 방제제 |
US6221890B1 (en) * | 1999-10-21 | 2001-04-24 | Sumitomo Chemical Company Limited | Acaricidal compositions |
US20040060246A1 (en) * | 2000-01-07 | 2004-04-01 | Nickell Craig A. | Insect control for buildings |
JP2004137150A (ja) * | 2002-08-20 | 2004-05-13 | Xyence Corp | 防蟻材料及びそれによる防蟻方法 |
US6667350B1 (en) * | 2002-10-17 | 2003-12-23 | Plymouth Foam, Incorporated | Calcium borate infused foam building materials and the like and method of making same |
JP2004269479A (ja) * | 2003-03-12 | 2004-09-30 | Otsuka Chemical Co Ltd | 殺ダニ剤組成物 |
MXPA06014862A (es) * | 2004-07-06 | 2007-03-21 | Basf Ag | Composiciones plaguicidas liquidas |
EP2235097B1 (de) * | 2007-12-21 | 2011-11-30 | Basf Se | Insektizid ausgerüstete partikel aus expandierbarem polystyrol und daraus erhältliche insektizid ausgerüstete formteile |
EP2230905A2 (de) * | 2007-12-21 | 2010-09-29 | Basf Se | Verfahren zur herstellung von insektizidausgerüsteten partikeln aus expandierbarem polystyrol, und hiervon erhältliche insektizidausgerüstete formteile |
-
2009
- 2009-10-21 BR BRPI0919713-3A patent/BRPI0919713A2/pt not_active IP Right Cessation
- 2009-10-21 US US13/124,979 patent/US20110201662A1/en not_active Abandoned
- 2009-10-21 KR KR1020117011527A patent/KR20110080169A/ko not_active Application Discontinuation
- 2009-10-21 AU AU2009306466A patent/AU2009306466A1/en not_active Abandoned
- 2009-10-21 EP EP09744660A patent/EP2355656A2/de not_active Withdrawn
- 2009-10-21 MX MX2011004119A patent/MX2011004119A/es unknown
- 2009-10-21 CN CN2009801519075A patent/CN102256483A/zh active Pending
- 2009-10-21 WO PCT/EP2009/063780 patent/WO2010046379A2/de active Application Filing
- 2009-10-21 JP JP2011532615A patent/JP2012506403A/ja not_active Withdrawn
- 2009-10-22 TW TW098135837A patent/TW201019853A/zh unknown
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WO2010046379A2 (de) | 2010-04-29 |
CN102256483A (zh) | 2011-11-23 |
TW201019853A (en) | 2010-06-01 |
AU2009306466A1 (en) | 2010-04-29 |
JP2012506403A (ja) | 2012-03-15 |
WO2010046379A3 (de) | 2011-05-05 |
BRPI0919713A2 (pt) | 2015-08-18 |
MX2011004119A (es) | 2011-05-04 |
KR20110080169A (ko) | 2011-07-12 |
US20110201662A1 (en) | 2011-08-18 |
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