EP1478690A1 - Mousses polymethacrylimides presentant une inflammabilite reduite et procede de fabrication - Google Patents
Mousses polymethacrylimides presentant une inflammabilite reduite et procede de fabricationInfo
- Publication number
- EP1478690A1 EP1478690A1 EP03742924A EP03742924A EP1478690A1 EP 1478690 A1 EP1478690 A1 EP 1478690A1 EP 03742924 A EP03742924 A EP 03742924A EP 03742924 A EP03742924 A EP 03742924A EP 1478690 A1 EP1478690 A1 EP 1478690A1
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- European Patent Office
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- meth
- composition
- Prior art date
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Classifications
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- 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
- C08J9/0014—Use of organic additives
- C08J9/0038—Use of organic additives containing phosphorus
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B2231/00—Material used for some parts or elements, or for particular purposes
- B63B2231/40—Synthetic materials
- B63B2231/50—Foamed synthetic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B5/00—Hulls characterised by their construction of non-metallic material
- B63B5/24—Hulls characterised by their construction of non-metallic material made predominantly of plastics
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T70/00—Maritime or waterways transport
- Y02T70/10—Measures concerning design or construction of watercraft hulls
Definitions
- the invention relates to compositions for the production of polymethacrylate foams with reduced flammability, polymethacrylimide molding compositions, polymethacrylimide foams and processes for the production of the above-mentioned products.
- Polymethacrylimide foams have been known for a long time and are widely used because of their excellent mechanical properties and their low weight, in particular in the production of layered materials, laminates, composites or foam composites. Prepregs are often combined with core materials made of polymethacrylimide.
- prepregs are used in aircraft construction, in shipbuilding, but also in buildings. For many of these numerous applications, they have to meet fire protection requirements, which are laid down in legal regulations and a number of other regulations.
- the proof that the foams meet the fire protection requirements is carried out with the aid of a large number of different fire tests, which are usually aimed at the use of the foam or the composite body containing it.
- the use of chlorine or bromine-containing compounds as flame retardants is widely known. These compounds are often used together with antimony oxides.
- the expandable graphite used for flame retardancy cannot be introduced homogeneously into the material, since the use of a disperser crushes the expandable graphite particles and thereby significantly reduces the flame retardant effect )
- the inhomogeneous foam sheets must be straightened manually, but this leads to a very high reject due to material breakage, ie -80% of the foam sheets produced cannot be used for application purposes.
- Another object of the invention was to provide low flammability polymethacrylimide foams which have reduced amounts of phosphorus compounds or halogenated hydrocarbons.
- the invention was also based on the object of specifying the most cost-effective flame retardant for polymethacrylimides and / or polymethacrylimide foams.
- the flame retardant used to finish the polymethacrylimides or the polymethacrylimide foams should be as safe as possible from a health point of view. Furthermore, the mechanical properties of the foams according to the invention should not be adversely affected by the additives. solution
- ammonium polyphosphate or combinations of ammonium polyphosphate and zinc sulfide are used as additives, PMI foams with a significantly reduced heat radiation according to FAR 25.853 (c) are obtained.
- the amount of ammonium polyphosphate alone, based on the total amount of monomers, is between 0.1 and 350% by weight ammonium polyphosphate, preferably between 5 and 200% by weight ammonium polyphosphate and very particularly preferably between 25 and 150% .-% ammonium polyphosphate.
- the amount of zinc sulfide alone, based on the total amount of monomers, is between 0.1-20% by weight zinc sulfide, preferably between 0.5-10% by weight zinc sulfide and very particularly preferably between 1-5 % By weight zinc sulfide
- the ammonium polyphosphate content is 1-300% by weight and zinc sulfide 0.1-20% by weight, preferably 5-200% by weight ammonium polyphosphate and zinc sulfide 0.5-10 % By weight and very particularly preferably between 25-150% by weight of ammonium polyphosphate and 1-5% by weight in the case of zinc sulfide.
- the use of these water-insoluble compounds as flame retardants for paints, synthetic resins and wood is known (Römpp, 10th edition, (1996), Ullmann, 4th edition (1979)).
- Additional flame retardants can optionally be used individually or in mixtures.
- phosphorus compounds such as phosphines, phosphine oxides, phosphonium compounds, phosphonates, phosphites or phosphates can be used as further flame retardants.
- the composition according to the invention can contain further flame retardants in order to additionally reduce the flammability.
- flame retardants are well known in the art.
- phosphorus-containing compounds can also be used. Compounds containing phosphorus are preferred due to the better recyclability of the plastics.
- the phosphorus compounds include, among others, phosphines, phosphine oxides, phosphonium compounds, phosphonates, phosphites and / or phosphates. These compounds can be organic and / or inorganic in nature, including derivatives of these compounds, such as, for example, phosphoric acid monoesters, phosphonic acid monoesters, phosphoric acid diesters, phosphonic acid diesters and phosphoric acid triesters, and also polyphosphates.
- Phosphorus compounds of the formula (I) are preferred.
- Examples of phosphorus compounds according to formula (I) include dimethylmethanephosphonate (DMMP), diethylmethanephosphonate, dimethylchloromethanephosphonate, diethylchloromethanephosphonate, dimethylhydroxymethanephosphonate, diethylhydroxymethanephosphonate, methoxycarbonylmethanephosphonatephosphonate ethyl methylesterphosphonate.
- DMMP dimethylmethanephosphonate
- diethylmethanephosphonate dimethylchloromethanephosphonate
- diethylchloromethanephosphonate diethylchloromethanephosphonate
- dimethylhydroxymethanephosphonate diethylhydroxymethanephosphonate
- methoxycarbonylmethanephosphonatephosphonate ethyl methylesterphosphonate methoxycarbonylmethanephosphonatephosphonate ethyl methylesterphosphonate.
- the phosphorus compounds can be used individually or as a mixture. Mixtures which contain phosphorus compounds of the formula (I) are particularly preferred.
- These compounds can be used in a proportion of up to 25% by weight, based on the weight of the monomers, in order to meet the fire protection standards.
- the proportion of phosphorus compounds is in the range from 1 to 15% by weight, without any intention that this should impose a restriction. If increasing amounts of these compounds are used, the other thermal and mechanical properties of the plastics, such as, for example, the compressive strength, the bending strength and the heat resistance, may deteriorate.
- compositions according to the invention for the production of poly (meth) acrylimide foams are polymerizable mixtures which comprise at least one, usually usually two or more monomers, such as (meth) acrylic acid and (meth) acrylonitrile, blowing agents, at least one polymerization initiator and ammonium polyphosphate and / or zinc sulfide as well as possibly contain other flame retardants. These compositions are polymerized to form precursors from which poly (meth) acrylimide foams are formed by heating.
- (meth) acrylic means acrylic, methacrylic and mixtures of the two.
- poly (meth) acrylimide foams obtainable from the compositions according to the invention have recurring units which can be represented by formula (II),
- R 1 and R 2 are the same or different hydrogen or a methyl group and R 3 is hydrogen or an alkyl or aryl radical having up to 20 carbon atoms.
- Units of structure (II) preferably form more than 30% by weight, particularly preferably more than 50% by weight and very particularly preferably more than 80% by weight of the poly (meth) acrylimide foam.
- the units of structural formula (II) can be formed from neighboring units of (meth) acrylic acid and (meth) acrylonitrile by heating to 150 to 250 ° C by a cyclizing isomerization reaction (cf. DE-C 18 17 156, DE -C 27 26 259, EP-B 146 892).
- a precursor is first by polymerizing the monomers in the presence of a radical initiator at low temperatures, e.g. B. 30 to 60 ° C with reheating to 60 to 120 ° C, which is then foamed by heating to about 180 to 250 ° C by a blowing agent contained (see EP-B 356 714).
- a radical initiator e.g. B. 30 to 60 ° C with reheating to 60 to 120 ° C, which is then foamed by heating to about 180 to 250 ° C by a blowing agent contained (see EP-B 356 714).
- a copolymer can first be formed which has (meth) acrylic acid and (meth) acrylonitrile, preferably in a molar ratio between 1: 4 and 4: 1.
- these copolymers can contain further monomer units which are obtained, for example, from esters of acrylic or methacrylic acid, in particular with lower alcohols having 1 to 4 carbon atoms, styrene, maleic acid or their anhydride, itaconic acid or their anhydride, vinylpyrrolidone, vinyl result in chloride or vinylidene chloride.
- the proportion of the comonomers which are difficult or difficult to cyclize should not exceed 30% by weight, preferably 20% by weight and particularly preferably 10% by weight, based on the weight of the monomers.
- crosslinking agents such as. B. allyl acrylate, allyl methacrylate, ethylene glycol diacrylate or dimethacrylate or polyvalent metal salts of acrylic or methacrylic acid, such as magnesium methacrylate can be used advantageously.
- the proportions of these crosslinkers are often in the range from 0.005 to 5% by weight, based on the total amount of polymerizable monomers.
- Metal salt additives can also be used. These include the acrylates or methacrylates of alkaline earth metals or zinc. Zn and Mg (meth) acrylate are preferred.
- the polymerization initiators used are those customary for the polymerization of (meth) acrylates, for example azo compounds, such as azodiisobutyronitrile, and peroxides, such as dibenzoyl peroxide or dilauroyl peroxide, or else other peroxide compounds, such as t-butyl peroctanoate or perketals, as well as optionally redox initiators (see also redox initiators) see, for example, H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylitatien, Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pages 286 ff, John Wiley & Sons, New York, 1978 ).
- the polymerization initiators are preferably used in amounts of 0.01 to 0.3% by weight, based on the total weight of the monomers used.
- polymerization initiators can also be advantageous to combine polymerization initiators with different disintegration properties with regard to time and temperature.
- it is well suited the simultaneous use of tert-butyl perpivalate, tert-butyl perbenzoate and tert-butyl per-2-ethylhexanoate or of tert-butyl perbenzoate, 2,2-azobisiso-2,4-dimethylvaleronitrile, 2,2-azobisisobutyronitrile and di-tert. butyl peroxide.
- the polymerization is preferably carried out via variants of bulk polymerization, such as, for example, combing / experiencing, without being limited to this.
- the weight average molecular weight M w of the polymers is preferably greater than 10 6 g / mol, in particular greater than 3x10 ⁇ g / mol, without any intention that this should impose a restriction.
- blowing agents are used to foam the copolymer during the conversion into an imide group-containing polymer form a gas phase up to 250 ° C by decomposition or evaporation.
- Blowing agents with an amide structure such as urea, monomethyl or N, N'-dimethylurea, formamide or monomethylformamide, release ammonia or amines upon decomposition, which can contribute to the additional formation of imide groups.
- nitrogen-free blowing agents such as formic acid, water or monohydric aliphatic alcohols having 3 to 8 carbon atoms, such as 1-propanol, 2-propanol, n-butan-1-ol, n-butan-2-ol, isobutan-1, can also be used -ol, isobutan-2-ol, tert. Butanol, pentanols and / or hexanols can be used.
- the amount of blowing agent used depends on the desired foam density, the blowing agents being used in the reaction mixture usually in amounts of about 0.5 to 15% by weight, based on the total weight of the monomers used.
- the preliminary products can also contain customary additives. These include, among other things, antistatic agents, antioxidants, mold release agents, lubricants, dyes, flame retardants, flow improvers, fillers, light stabilizers and organic phosphorus compounds such as phosphites or phosphonates, pigments, release agents, weathering protection agents and plasticizers.
- customary additives include, among other things, antistatic agents, antioxidants, mold release agents, lubricants, dyes, flame retardants, flow improvers, fillers, light stabilizers and organic phosphorus compounds such as phosphites or phosphonates, pigments, release agents, weathering protection agents and plasticizers.
- Conductive particles that prevent the foams from becoming electrostatically charged are another class of preferred additives. These include metal and soot particles, which can also be present as fibers, with a size in the range of 10 nm and 10 mm, as described in EP 0 356 714 A1.
- anti-settling agents are preferred additives because these substances effectively stabilize the compositions for the production of polyacrylimide foams.
- These include carbon blacks, for example KB EC-600 JD from Akzo Nobel, and Aerosile, for example Aerosil 200 from De- gussa AG, or polymer-based thickeners, such as high-molecular polymethyl methacrylate.
- a poly (meth) acrylimide foam according to the invention can be produced, for example, by mixing a mixture of
- component (A) 0-20% by weight of further vinylically unsaturated monomers, the constituents of component (A) giving 100% by weight;
- (C) 1-50% by weight, based on the weight of components (A), ammonium polyphosphate and / or zinc sulfide.
- thermoplastically processable molding compositions have poly (meth) acrylimides with high heat resistance, which can be obtained, for example, by reacting polymethyl methacrylate or its copolymers with primary amines.
- Representative of the large number of examples of this polymer-analogous imidation may be mentioned: US 4,246,374, EP 216 505 A2, EP 860 821.
- High heat resistance can be achieved either by using arylamines (JP 05222119 A2) or by using special comonomers (EP 561 230 A2, EP 577 002 A1). All of these reactions result in solid polymers which can be foamed to obtain a foam in a separate second step, with suitable techniques known to those skilled in the art.
- Poly (meth) acrylimide molding compositions according to the invention contain, as an essential component, flame-retardant ammonium polyphosphate and / or zinc sulfide. This component is preferably used in the amounts set out above.
- these molding compositions can have the optional additives mentioned above. They can be equipped with ammonium polyphosphate and / or zinc sulfide before, during or after the polymerization or imidation using known processes.
- these molding compositions can be foamed using known techniques.
- the previously mentioned blowing agents can be used, which can be added to the molding compositions, for example, by compounding.
- Poly (meth) acrylimide foams according to the invention can be provided with cover layers, for example to increase the strength.
- layer materials are known which offer a certain level of flame protection simply by choosing the covering material.
- the fire protection achieved by using these composite materials can be significantly improved.
- Any known flat structure can be used as the cover layer, which is stable in the processing parameters required for producing the composite structure, such as pressure and temperature.
- films and / or sheets which polypropylene, polyester, polyether, polyamide, polyurethane, polyvinyl chloride, polymethyl (meth) acrylate, by curing reaction resins, such as epoxy resins (EP resins), methacrylate resins (MA resins), unsaturated Polyester resins (UP resins), isocyanate resins and phenacrylate resins (PHA resins), bismaleimide resins and phenolic resins, plastics and / or metals obtained, such as aluminum, for example.
- mats or webs can preferably be used as the top layer, which comprise glass fibers, carbon fibers and / or aramid fibers, wherein webs which have a multilayer structure can also be used as the top layer.
- These fibrous webs can be applied to the foams, among other things, as prepregs.
- carbon fiber reinforced plastics are also known which are particularly suitable as cover layers.
- the thickness of the cover layer is preferably in the range from 0.1 to 100 mm, preferably in the range from 0.5 to 10 mm.
- An adhesive can also be used to improve adhesion. Depending on the material of the cover layer, this is not necessary.
- the poly (meth) acrylimide foams according to the invention and in particular the layer materials containing these foams can for example used in aircraft construction and for the construction of ships or rail vehicles.
- the foams produced in this way also pass the flue gas density test in accordance with FAR 25.853 (c), AITM 2.0007, the requirement for the vertical flame test in accordance with FAR 25.853 (a) (1) (i) and the toxicity requirement in accordance with AITM 3.0005. Contrary to the systems filled with expanded graphite, a homogeneous particle distribution is possible, so that these foam sheets can be processed according to the generally known possibilities with regard to the commercially available PMI foams.
- the foam thus obtained had a density of 72 kg / m 3 .
- the foam produced in this way also passes the flue gas density test according to FAR 25.853 (c), AITM 2.0007, the requirement of the vertical flame test according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005.
- tert-butyl perbenzoate 400 g (4.0 parts by weight) Degalan BM 310 (high molecular weight polymethyl methacrylate), 0.5 g (0.005 parts by weight) benzoquinone and 32.0 g (0.32 parts by weight) Parts) PAT 1037 added as a release agent.
- the foam produced in this way also passes the flue gas density test according to FAR 25.853 (c), AITM 2.0007, the requirement of the vertical flame test according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005.
- the foam thus obtained had a density of 78 kg / m 3 .
- the foam thus produced also passes the flue gas density test in accordance with FAR 25.853 (c), AITM 2.0007, the requirement for the vertical flame test in accordance with FAR 25.853 (a) (1) (i) and the toxicity requirement in accordance with AITM 3.0005.
- the foam thus obtained had a density of 76 kg / m 3 .
- the foam thus produced also passes the smoke gas density test in accordance with FAR 25.853 (c), AITM 2.0007, the requirement of vertical flame mung tests according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005.
- the foam thus obtained had a density of 79 kg / m 3 .
- the foam produced in this way also passes the flue gas density test according to FAR 25.853 (c), AITM 2.0007, the requirement of the vertical flame test according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005.
- the foam thus obtained had a density of 77 kg / m 3 .
- the foam produced in this way also passes the flue gas density test according to FAR 25.853 (c), AITM 2.0007, the requirement of the vertical flame test according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005.
- Methacrylonitrile (50.0 parts by weight) 1000 g (10.0 parts by weight) important parts) isopropanol added.
- the mixture was further mixed with 20 g (0.20 parts by weight) of tert-butyl perpivalate, 3.6 g (0.036 parts by weight) of tert-butyl per-2-ethylhexanoate, 10 g (0.10 parts by weight).
- Parts) tert-butyl perbenzoate 500 g (5.0 parts by weight)
- Degalan BM 310 high molecular weight polymethyl methacrylate
- 0.5 g (0.005 parts by weight) benzoquinone
- 32.0 g (0.32 parts by weight) Parts) PAT 1037 added as a release agent.
- APP2 ammonium polyphosphate
- Nordmann, Rassmann GmbH & Co. 10,000 g (100.0 parts by weight) of APP2 (ammonium polyphosphate) from Nordmann, Rassmann GmbH & Co. were added to the mixture as a flame retardant.
- the mixture was stirred until homogenized and then polymerized at 19.5 h at 50 ° C. in a chamber formed from two glass plates of size 50 ⁇ 50 cm and a 1.85 cm thick edge seal.
- the polymer was then subjected to a tempering program ranging from 40 ° C. to 115 ° C. for 17.25 hours. The subsequent foaming took place at 185 ° C. for 2 hours.
- the foam thus obtained had a density of 66 kg / m 3 .
- the foam produced in this way also passes the flue gas density test according to FAR 25.853 (c), AITM 2.0007, the requirement of the vertical flame test according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005.
- APP2 ammonium polyphosphate
- Nordmann, Rassmann GmbH & Co. 5,000 g (50.0 parts by weight) of APP2 (ammonium polyphosphate) from Nordmann, Rassmann GmbH & Co. were added to the mixture as flame retardants.
- the mixture was stirred until homogenized and then polymerized at 65 ° C. at 45 ° C. in a chamber formed from two 50 ⁇ 50 cm glass plates and a 1.85 cm thick edge seal.
- the polymer was then subjected to a tempering program ranging from 40 ° C. to 115 ° C. for 17.25 hours. The subsequent foaming took place at 196 ° C. for 2 hours.
- the foam thus obtained had a density of 69 kg / m 3 .
- the foam produced in this way also passes the flue gas density test according to FAR 25.853 (c), AITM 2.0007, the requirement of the vertical flame test according to FAR 25.853 (a) (1) (i) and the toxicity requirement according to AITM 3.0005. Comparative Example 1
- a foam with a density of 71 kg / m3 was produced in accordance with DE 33 46 060, 10 parts by weight of DMMP being used as the flame retardant.
- DMMP dimethyl methane phosphonate
- the mixture contained 20 g (0.20 part by weight) of release agent (MoldWiz) and 70 g (0.70 part by weight) of ZnO.
- This mixture was polymerized for 92 hours at 40 ° C. in a chamber formed from two glass plates measuring 50 ⁇ 50 cm and a 2.2 cm thick edge seal. The polymer was then subjected to a tempering program ranging from 40 ° C. to 115 ° C. for 17.25 hours. The subsequent foaming took place at 215 ° C. for 2 hours. The foam thus obtained had a density of 71 kg / m 3 .
- the foam thus produced also does not pass the flue gas density test in accordance with FAR 25.853 (c), AITM 2.0007 and also does not pass the requirement for the vertical flame test in accordance with FAR 25.853 (a) (1) (i)
- DMMP dimethyl methane phosphonate
- the procedure was essentially as in the case of Comparative Example 1, except that the foaming was carried out at 210 ° C. and the density of the foam obtained was then 110 kg / m 3 .
- the foam thus produced also does not pass the smoke gas density test in accordance with FAR 25.853 (c), AITM 2.0007.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
La présente invention concerne des compositions destinées à la fabrication de mousses poly(méth)acrylimides présentant une inflammabilité réduite, contenant des polyphosphates d'ammonium et/ou du sulfure de zinc. L'invention concerne également des matières à mouler poly(méth)acrylimides ainsi que des mousses poly(méth)acrylimides pouvant être obtenues à partir desdites compositions et matières à mouler. L'invention concerne également des procédés de fabrication de mousses poly(méth)acrylimides présentant une inflammabilité réduite.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10208684 | 2002-02-28 | ||
DE10208684 | 2002-02-28 | ||
DE10217005 | 2002-04-16 | ||
DE10217005A DE10217005A1 (de) | 2002-02-28 | 2002-04-16 | Polymethacrylimid-Schaumstoffe mit verminderter Entflammbarkeit sowie Verfahren zur Herstellung |
PCT/EP2003/000337 WO2003072647A1 (fr) | 2002-02-28 | 2003-01-15 | Mousses polymethacrylimides presentant une inflammabilite reduite et procede de fabrication |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1478690A1 true EP1478690A1 (fr) | 2004-11-24 |
Family
ID=27766686
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03742924A Withdrawn EP1478690A1 (fr) | 2002-02-28 | 2003-01-15 | Mousses polymethacrylimides presentant une inflammabilite reduite et procede de fabrication |
Country Status (11)
Country | Link |
---|---|
US (1) | US20050090568A1 (fr) |
EP (1) | EP1478690A1 (fr) |
JP (1) | JP2005526871A (fr) |
CN (1) | CN1610719A (fr) |
AU (1) | AU2003248332A1 (fr) |
BR (1) | BR0307934A (fr) |
CA (1) | CA2471317A1 (fr) |
MX (1) | MXPA04008343A (fr) |
NO (1) | NO20044094L (fr) |
RU (1) | RU2004128950A (fr) |
WO (1) | WO2003072647A1 (fr) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10141757A1 (de) * | 2001-08-29 | 2003-03-27 | Roehm Gmbh | Verbessertes Verfahren zur Herstellung von PMI-Schäumen |
DE10259674A1 (de) * | 2002-12-18 | 2004-07-15 | Röhm GmbH & Co. KG | Derivatisierung hochmolekularer Polymethacrylimide |
US8722751B2 (en) * | 2003-10-30 | 2014-05-13 | Evonik Rohm Gmbh | Thermostable microporous polymethacrylimide foams |
DE102007033120A1 (de) * | 2007-07-13 | 2009-01-15 | Evonik Röhm Gmbh | Verbesserte Stumpfstoßverbindungen für Kernwerkstoffe |
CN101381427B (zh) * | 2007-09-04 | 2013-06-26 | 赢创罗姆有限公司 | 制备块状聚(甲基)丙烯酰亚胺泡沫材料的方法 |
FR2922188B1 (fr) * | 2007-10-11 | 2010-04-23 | Airbus France | Cale en materiau composite renforcee et procede de renforcement d'une cale en materiau composite |
DE102008001695A1 (de) | 2008-05-09 | 2009-11-12 | Evonik Röhm Gmbh | Poly(meth)acrylimide mit verbesserten optischen und Farbeigenschaften, insbesondere bei thermischer Belastung |
DE102010028695A1 (de) * | 2010-05-06 | 2011-11-10 | Evonik Röhm Gmbh | Polymethacrylimid-Schaumstoffe mit verminderter Entflammbarkeit sowie Verfahren zur Herstellung dieser |
DE102010040286A1 (de) * | 2010-08-31 | 2012-03-01 | Evonik Röhm Gmbh | PMI-Schäume mit verbesserten mechanischen Eigenschaften, insbesondere mit erhöhter Reißdehnung |
JP5957252B2 (ja) * | 2012-03-21 | 2016-07-27 | 積水化成品工業株式会社 | アクリル系樹脂発泡体の製造方法 |
DE102012208428A1 (de) * | 2012-05-21 | 2013-11-21 | Evonik Industries Ag | Pul-Core-Verfahren mit PMI-Schaumkern |
CN103539890A (zh) * | 2013-10-23 | 2014-01-29 | 江苏兆鋆新材料科技有限公司 | 一种无卤阻燃型an/maa共聚物泡沫材料的制备方法 |
DE102013225132A1 (de) * | 2013-12-06 | 2015-06-11 | Evonik Industries Ag | Vorschäumung von Poly(meth)acrylimid-Partikeln für das anschließende Formschäumen in geschlossenen Werkzeugen |
CN104017127B (zh) * | 2014-06-20 | 2016-08-17 | 江苏兆鋆新材料股份有限公司 | 一种耐高温无卤阻燃树脂添加型an/maa共聚物泡沫及其制备方法 |
CN104045764B (zh) * | 2014-06-23 | 2016-04-13 | 浙江理工大学 | 一种聚甲基丙烯酰亚胺泡沫塑料的制备方法 |
BR112017012088A2 (pt) * | 2014-12-22 | 2018-01-16 | Dow Global Technologies Llc | polímeros de imida polimetacrílica-ácido e métodos de preparar e usar os mesmos |
CN104610562B (zh) * | 2015-02-15 | 2016-03-30 | 浩博(福建)新材料科技有限公司 | 一种聚甲基丙烯酰亚胺泡沫的制备方法 |
CN106279498A (zh) * | 2016-08-16 | 2017-01-04 | 湖南兆恒材料科技有限公司 | 一种高性能pmi泡沫及其制备方法 |
WO2018048946A1 (fr) * | 2016-09-06 | 2018-03-15 | The Patent Well LLC | Matériau d'étanchéité possédant des propriétés de résistance au feu destiné à être utilisé avec des pièces d'aéronef |
CN107417846A (zh) * | 2017-08-31 | 2017-12-01 | 湖南和铸新材料科技有限公司 | 聚甲基丙烯酰亚胺泡沫塑料及其制备方法 |
WO2019173479A1 (fr) * | 2018-03-06 | 2019-09-12 | The Patent Well LLC | Bagues d'étanchéité en caoutchouc mousse pelliculées et ruban ignifuge, à limites de densité de fumée et de toxicité |
CN110317362B (zh) * | 2019-07-10 | 2022-04-19 | 湖南兆恒材料科技有限公司 | 一种电子音响用pmi泡沫材料及其制备方法 |
CN110804121B (zh) * | 2019-11-19 | 2021-11-30 | 湖南博翔新材料有限公司 | 一种低烟低毒高阻燃性聚甲基丙烯酰亚胺泡沫 |
CN111087735B (zh) * | 2019-12-24 | 2022-03-08 | 安徽昌发实业有限公司 | 一种家具生产用抗压防变型保温材料 |
CN115466476A (zh) * | 2022-09-20 | 2022-12-13 | 湖南兆恒材料科技有限公司 | 一种具有吸波性能和阻燃性能的pmi泡沫制备方法 |
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DE3346060A1 (de) * | 1983-12-21 | 1985-07-04 | Röhm GmbH, 6100 Darmstadt | Flammgeschuetzter polyacryl- oder polymethacrylimidschaumstoff und verfahren zu seiner herstellung |
DE19541037A1 (de) * | 1995-11-03 | 1997-05-07 | Hoechst Ag | Halogenfreier, flammwidriger Polyurethanhartschaum |
DE19606530C2 (de) * | 1996-02-22 | 1998-04-02 | Roehm Gmbh | Verfahren zur Herstellung von Polymethacrylimid-Schaumstoffen mit flammhemmenden Zusätzen und danach hergestellte Schaumstoffe |
DE19717483C2 (de) * | 1997-04-25 | 2000-05-04 | Roehm Gmbh | Polymethacrylimid-Schaumstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19843595C2 (de) * | 1998-09-23 | 2003-05-22 | Sachtleben Chemie Gmbh | Flammschutzmittel und deren Verwendung |
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2003
- 2003-01-15 RU RU2004128950/04A patent/RU2004128950A/ru not_active Application Discontinuation
- 2003-01-15 CN CNA038018233A patent/CN1610719A/zh active Pending
- 2003-01-15 MX MXPA04008343A patent/MXPA04008343A/es unknown
- 2003-01-15 WO PCT/EP2003/000337 patent/WO2003072647A1/fr not_active Application Discontinuation
- 2003-01-15 JP JP2003571346A patent/JP2005526871A/ja active Pending
- 2003-01-15 BR BR0307934-1A patent/BR0307934A/pt not_active Application Discontinuation
- 2003-01-15 CA CA002471317A patent/CA2471317A1/fr not_active Abandoned
- 2003-01-15 EP EP03742924A patent/EP1478690A1/fr not_active Withdrawn
- 2003-01-15 AU AU2003248332A patent/AU2003248332A1/en not_active Abandoned
- 2003-01-15 US US10/498,973 patent/US20050090568A1/en not_active Abandoned
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US20050090568A1 (en) | 2005-04-28 |
WO2003072647A1 (fr) | 2003-09-04 |
RU2004128950A (ru) | 2005-05-27 |
CA2471317A1 (fr) | 2003-09-04 |
MXPA04008343A (es) | 2004-11-26 |
CN1610719A (zh) | 2005-04-27 |
JP2005526871A (ja) | 2005-09-08 |
BR0307934A (pt) | 2004-12-21 |
NO20044094L (no) | 2004-11-18 |
AU2003248332A1 (en) | 2003-09-09 |
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