WO2010149441A1 - Procédé de fabrication d'une pièce en mousse à partir de poly(méth)acrylates réticulés ainsi que ladite mousse et ses utilisations - Google Patents
Procédé de fabrication d'une pièce en mousse à partir de poly(méth)acrylates réticulés ainsi que ladite mousse et ses utilisations Download PDFInfo
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- WO2010149441A1 WO2010149441A1 PCT/EP2010/057072 EP2010057072W WO2010149441A1 WO 2010149441 A1 WO2010149441 A1 WO 2010149441A1 EP 2010057072 W EP2010057072 W EP 2010057072W WO 2010149441 A1 WO2010149441 A1 WO 2010149441A1
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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
- C08J9/04—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
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- 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
- C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
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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
- 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
- C08J2333/04—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 esters
- C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
Definitions
- the invention relates to a method for producing a foam part, in particular a closed-cell foam part, by expansion from prepolymers of crosslinked poly (meth) acrylates, which are produced by Gußpolymerisations vide.
- Plastic rigid foams have been known for a long time and are widely used because of their excellent mechanical properties and low weight, especially in the manufacture of laminates, laminates, composites or foam composites.
- cover layers z. B. made of carbon fibers with the help of adhesive resins form-fitting and permanently connected to core materials made of hard foams.
- hard foams z. Poly (meth) acrylimide foams under the brand ROHACELL ® from Evonik put on the market.
- coating materials are used as stiff, lightweight components in aircraft construction, in shipbuilding, in the automotive industry or in the wings of wind power plants.
- the invention relates to a method for producing a foam part, in particular a closed-cell foam part, by expansion from prepolymers of crosslinked poly (meth) acrylates, which are produced by Gußpolymerisations vide.
- Poly (meth) acrylates in the context of the invention are polymers which are predominantly, for. B. to at least 60, at least 70, at least 80, at least 90 wt .-%, or entirely composed of polymethylated acrylates and / or methacrylates and optionally may also contain minor amounts of comonomers that are not (meth) acrylates.
- (Meth) acrylates are understood to mean both acrylic acid and methacrylic acid and derivatives thereof.
- prepolymer within the meaning of the invention denotes the claimed polymerized monomer mixture, which is present before the foaming in the form of a solid plastic part.
- the Pre-Polymehsate is thus an intermediate polymer or not (not yet) foamed plastic body.
- Crosslinked poly (meth) acrylates are, in particular, crosslinked polymethyl (meth) acrylates or crosslinked poly (meth) acrylimides. Prepolymer of crosslinked polymethyl (meth) acrylates
- Pre-polymers of crosslinked polymethyl (meth) acrylates in the context of the invention are obtainable by polymerization of a polymerizable monomer mixture, which is composed essentially of methyl methacrylate as a non-crosslinking (meth) acrylate monomers, crosslinkers and an initiator system, in Gußpolymerisations vide.
- blowing agents which are not inert gases may additionally be present in the polymerizable monomer mixture.
- a suitable polymerizable monomer mixture for polymethyl (meth) acrylates may for example consist of:
- crosslinkers 0.01 -10% by weight of crosslinkers
- Suitable further vinylically unsaturated non-crosslinking monomers are, for. Methacrylic acid and esters of methacrylic acid (eg, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate), acrylic acid and esters of acrylic acid (eg, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate) or styrene and styrene derivatives such as ⁇ - Methylstyrene or p-methylstyrene, and methacrylonitrile and acrylonitrile, methacrylamide and acrylamide and substituted methacrylamides and substituted acrylamides.
- methacrylic acid and esters of methacrylic acid eg, ethyl methacrylate, butyl methacrylate, hexyl me
- crosslinkers examples include (meth) acrylic esters of diols, such as, for example, ethylene glycol dimethacrylate or 1,4-butanediol dimethacrylate, aromatic compounds having two vinyl or allyl groups, for example divinylbenzene, or other crosslinkers having two ethylenically unsaturated, radically polymerizable radicals, such as, for example, B. allyl methacrylate used.
- crosslinkers containing three or more unsaturated, free-radically polymerizable groups such as allyl groups or (meth) acrylic groups
- suitable crosslinkers containing three or more unsaturated, free-radically polymerizable groups include thallyl cyanurate, trimethylolpropane triacrylate and trimethacrylate and pentaerythritol tetraacrylate and tetramethacrylate.
- Other examples are z. As indicated in US 4,513,118.
- ionic crosslinkers are polyvalent metal cations that form ionic bridges between the acid groups of the copolymers. Examples include the acrylates or methacrylates of the alkaline earth metals or zinc. Zn and Mg (meth) acrylates are preferred. The (meth) acrylate salts can also be prepared by dissolving, for example, ZnO or MgO in the monomer batch.
- the use of ionic crosslinkers requires that acid group-containing monomers, for. As acrylic acid or preferably methacrylic acid are copolymerized with. Polymerization initiators for polymethyl (meth) acrylates
- the polymerization is generally started with known free-radical initiators.
- the preferred initiators include the azo initiators well known in the art, such as AIBN and IJ azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, di-tert-butyl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, Methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert
- These compounds are often used in an amount of 0.01 to 5 wt .-%, preferably from 0.5 to 3 wt .-%, based on the weight of the monomers.
- auxiliaries or additives are known to the person skilled in the art. These include, for example, antistatics, antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers, UV absorbers and organic phosphorus compounds, such as phosphites or phosphonates, pigments, weathering agents and plasticizers. Further blowing agents for polymethyl (meth) acrylates
- the polymerizable monomer mixture may additionally contain further blowing agents.
- the other blowing agents are different from the inert gases, which are also used in the context of the invention as a blowing agent. However, it is preferred to add to the polymerizable monomer mixture no or only insignificant amounts of further blowing agents.
- einpolymer isomers blowing agent may tert-butyl methacrylate or tert-butyl acrylate called. When used as comonomers, these compounds split off the propellant isobutene when the prepolymer is heated.
- Pre-polymers of crosslinked poly (meth) acrylimides in the context of the invention are formed by thermal conversion of crosslinked copolymers of methacrylic acid and methacrylonitrile. In thermal conversion, about 60 to 80% of the methacrylic and methacrylic units become cyclic Implemented imide structures. In the polymer are unreacted methacrylic acid and methacrylonitrile units, as well as additionally cyclic anhydride structures, polyimine ladder polymer units.
- the crosslinked copolymers of methacrylic acid and methacrylonitrile are obtained by polymerization in Gußpolymerisationsclar a polymerizable monomer mixture, which is composed essentially of methacrylic acid and methacrylonitrile as non-crosslinking (meth) acrylate monomers, crosslinkers and an initiator system.
- blowing agents which are not inert gases may additionally be present in the polymerizable monomer mixture.
- a suitable polymerizable monomer mixture for poly (meth) acrylimides may for example consist of:
- crosslinker 0.01 -10% by weight of crosslinker
- vinylically unsaturated monomers may be present: acrylic or methacrylic acid and esters thereof with lower alcohols having 1-4 C atoms, styrene, maleic acid or its anhydride, itaconic acid or its anhydride, Vinylpyrrolidone, vinyl chloride and / or vinylidene chloride.
- the proportion of comonomers which can not or only with great difficulty be cyclized to anhydride or imide should not exceed 30% by weight, preferably 20% by weight and more preferably 10% by weight, based on the weight of the monomers ,
- the formulations must be added small amounts of crosslinker. Suitable amounts are for. B. 0.01 to 10, 0.01 to 2, 0.01 to 0.5 wt .-% based on the total weight of the monomer mixture.
- a slight cross-linking stabilizes the foam during the foaming process and thus enables the production of homogeneous foams. At the same time, the heat resistance and the creep behavior of the foam are improved by crosslinking agents.
- crosslinkers can be divided into two groups: covalent crosslinkers and ionic crosslinkers.
- Covalent crosslinkers are copolymerizable polyunsaturated compounds. As such monomers z. Allyl acrylate, allyl methacrylate, allylacrylamide, allylmethacrylamide, methylenebisacrylamide or methacrylamide, diethylenebis (allylcarbonate), ethylene glycol diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, triethylene glycol diacrylate or dimethacrylate, tetraethylene glycol diacrylate or dimethacrylate, tripropylene glycol diacrylate or dimethacrylate, 1,3-butanediol diacrylate or dimethacrylate, 1,4-butanediol diacrylate or dimethacrylate, neopentyl diol diacrylate or dimethacrylate, hexanediol 1,6-diacrylate or dim
- ionic crosslinkers are polyvalent metal cations that form ionic bridges between the acid groups of the copolymers. Examples include the acrylates or methacrylates of the alkaline earth metals or zinc. Zn and Mg (meth) acrylates are preferred. The (meth) acrylate salts can also be obtained by dissolving e.g. be prepared by ZnO or MgO in the monomer mixture.
- the use of ionic crosslinkers requires that acid group-containing monomers, for. As acrylic acid or preferably methacrylic acid with einpolymehsiert.
- initiators compounds and initiator systems that can initiate radical polymerizations are used.
- Known classes of compounds are peroxides, hydroperoxides, peroxodisulfates, percarbonates, perketals, peroxyesters, hydrogen peroxide and azo compounds.
- initiators are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxodicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide, acetyl acetone peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroctanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate, azoisobutyronitrile, 2.2 Azobisiso-2,4-dimethylvaleronitrile, 2,2-azobisisobutyronitrile, 2,2'-azobis (2-ami
- redox initiators H. Rauch-Puntigam, Th. Völker, acrylic and methacrylic compounds, Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pages 286 et seq., John Wiley & Sons, 1 New York, 1978. It may be beneficial to combine initiators and initiator systems having different disintegration properties with respect to time and temperature.
- the initiators are used in amounts of 0.01 to 2 wt .-%, particularly preferably from 0.15 to 1, 5 wt .-% based on the total weight of the monomer mixture.
- additives can be added to the mixtures. Suitable amounts are for. B. 0 to 20, 0 to 10 or 0 to 5 wt .-% based on the monomer mixture.
- the usual additives are different from the monomers mentioned, crosslinkers, blowing agents or initiators.
- Phosphorus compounds are preferred because of lower smoke toxicity in case of fire. Phosphorus compounds include, but are not limited to, phosphines, phosphine oxides, phosphonium compounds, Phosphonates, phosphites and / or phosphates.
- These compounds may be of organic and / or inorganic nature, such as, for example, phosphoric acid monoesters, phosphonic acid monoesters, phosphoric diesters, phosphonic diesters and phosphoric acid triesters, and also polyphosphates.
- the polymerizable monomer mixture may additionally contain further blowing agents.
- the other blowing agents are different from the inert gases, which are also used in the context of the invention as a blowing agent. However, it is preferred to add to the polymerizable monomer mixture no or only insignificant amounts of further blowing agents.
- einpolymer isdes blowing agent may tert-butyl methacrylate or tert-butyl acrylate called. When used as comonomers, these compounds split off the propellant isobutene when the prepolymer is heated. Inert gas as propellant
- the blowing agent used is an inert gas.
- Inert gases in the context of the invention are gases which undergo no chemical reactions with the pre-polymer even at elevated pressure and elevated temperature.
- a series of gases, such as As hydrogen, propane, butane or pentane, which meet this requirement, are from a practical point of view, increased plant engineering effort to ensure the explosion protection, little suitable, but should not be excluded from the scope therefore already.
- Particularly preferred are nitrogen or carbon dioxide.
- an increase in volume z. B. by a factor of 5 to 100, preferably by a factor of 8 to 30.
- an increase in volume by a factor greater than zero to 4, preferably from 0.5 to 3 understood.
- the outstanding mechanical properties of the foam part produced according to the invention result, in particular, from the comparatively high molecular weight of the prepolymer.
- the comparatively high molecular weight of Prepolymehsats is due to its production in Gußpolymerisations vide. Since the pre-polymer has a virtually infinite molecular weight owing to its crosslinking, its molecular weight is approximately given by the molecular weight of the molecular chains in the uncrosslinked state. These are considerably longer than molecular weights of molecular chains which are obtained in other processes, for example in the polymerization of molding compositions.
- the molecular weight of the prepolymer can be characterized by a molecular weight M w (weight average) of at least 1,000,000, preferably at least 3,000,000 g / mol, which is obtained on polymerization of the monomer mixture under otherwise identical conditions but without the crosslinker.
- the molecular weight M w (weight average) can be determined, for example, by gel permeation chromatography or by scattered light method (see, for example, BHF Mark et al., Encyclopaedia of Polymer Science and Engineering, 2nd Edition, Vol , 1989).
- the process step (a) comprises the polymerization of a polymerizable monomer mixture, which consists essentially of non-crosslinking (meth) acrylate monomers, crosslinkers and an initiator system, in the Gusspolymehsations compiler to a pre-polymer.
- the casting polymerization process is well known to those skilled in the art and may, for example, be as follows
- the polymerization chamber in which the polymehsierbare liquid is polymerized, is usually a flat chamber. This consists z. B. from two plane-parallel mold plates and a spacer plates sealing the mold plates. This may be an elastic cord or an elastic seal.
- the liquid to be polymerized (see, for example, the polymerization of methyl methacrylate in the chamber process: Vieweg Esser, Plastics Handbook, Volume 9, pages 43 to 55, Carl Hanser, Kunststoff 1975) is in the sealed on three sides, optionally evacuated chamber of the still open fourth page ago filled.
- the polymerization is usually carried out in such an arrangement of the chambers, which ensures a temperature control or heat dissipation, so can - lying horizontally in racks - chambers, for example in hot air ovens at high air velocity, in autoclaves using water spray or in water-filled tanks under polymerization being held.
- the polymerization is initiated by heating and / or by irradiation.
- the polymerization temperatures are usually between 15 and 70 0 C at atmospheric pressure. In the autoclave, they are expediently about 90 to 100 ° C.
- the residence time of the polymerization chamber in the temperature control medium varies according to the manner of the polymerization batch and the reaction between a few hours and several days.
- the temperature can be increased again for a short time towards the end of the polymerization, for example to above 100 0 C, about 120 0 C. It is expedient to cool slowly, with the polymer plates separated from the mold plates and can be removed.
- Process step (b) comprises loading the prepolymer with an inert gas as blowing agent at a pressure in the range from 2 to 200, preferably 2 to 50, in particular 4 to 30, bar.
- the loading can take place in a pressure chamber or in an autoclave.
- the inert gas diffuses into the prepolymer.
- the loading of the prepolymer is preferably carried out at elevated temperature.
- the loading of the Pre-Polymehsat with the inert gas at a temperature which is lower by 50 0 C or above the softening temperature of the prepolymer.
- the softening temperature is understood in particular to mean the Vicat softening temperature VET (ISO 306-B50).
- the softening temperature or VET of crosslinked poly (meth) acrylates is typically in the range of about 120 ° C.
- the loading therefore takes place in the range from 70 to 170 ° C.
- the softening temperature VET or the crosslinked poly (meth) acrylimides is typically in the range of about 170 0 C.
- the loading is therefore in the range from 120 to 220 0 C.
- the duration of the loading depends on the temperature. As a guide value depending on the temperature, the pressure and the thickness or the specific surface of the pre-polymer z. B. 6 to 24 hours. The higher the temperature, the softer the prepolymer and the lower the loading time. The Pre-Polymehsat must not be too soft, as it is Otherwise, for example, could stick to the autoclave wall, which hinders the process. A person skilled in the art can, with knowledge of the present invention, choose favorable pressures, temperatures and loading times for specific pre-polymers or determine them experimentally.
- the process step (b) and the process step (c) can be carried out in spatially separated equipment, which contributes to a better overall system utilization and cost reduction.
- the process step (c) comprises lowering the pressure and expanding the pre-polymer slurry to the foam part at a temperature at which the propellant-loaded pre-polymerate is foamable.
- the temperature at which the propellant loaded pre-polymerisate is foamable depends on a number of factors.
- the consistency and foamability of the prepolymer depends on its composition. The lower the degree of crosslinking, the easier the foamability. The higher the temperature, the softer the prepolymer and the easier it is to foam.
- the pressure in turn acts as a counterforce to the foaming force. In addition, the pressure counteracts the outdiffusion of the inert gas and it is achieved the formation of only a thin foam skin.
- Foaming skin refers to a near-surface area of the foam part with a significantly increased density. The foaming skin is therefore separated as waste. It is therefore desirable to keep foaming skin as low as possible.
- the suitable temperature ranges therefore extend over a wide range from about 50 to 250, preferably 100 to 220 ° C.
- a temperature range at which the propellant-loaded pre-polymer of crosslinked poly (meth) acrylates can be foamed can, for. B. roughly 50 to 180, preferably with 100 to 150 0 C are given.
- a temperature range at which the propellant-loaded pre-polymer of crosslinked poly (meth) acrylimides is foamable can, for. B. roughly with 100 to 250, preferably with 150 to 220 0 C.
- the expansion of the prepolymer to the foam part preferably takes place at a lower pressure than during the loading of the prepolymer but above the normal pressure. This allows better control over the expansion process and avoids uncontrolled foaming which leads to irregular foam structures.
- the polymerizable monomer mixture may additionally contain further blowing agents.
- pressure and temperature can be lowered after the loading of the plastic molding with the inert gas, so that no or only a slight expansion of the pre-polymer occurs.
- the final expansion is effected by raising the temperature without raising the pressure, wherein the foaming force is at least partially due to the additional blowing agent. This is advantageous because a control of the average pore diameter can be made so.
- the process step (d) comprises the fixation of the foam part by lowering the temperature. After expansion, the foamed state is fixed.
- the finished foam can be removed from the equipment and is ready for refining by separation of the foam skins and further confectioning steps or in particular for further processing into core materials for sandwich constructions of all kinds. foam piece
- foam parts of crosslinked poly (meth) acrylates can be produced.
- a poly (meth) acrylimidschaums is preferably in the range of 20 kg / m 3 to 320 kg / m 3 , more preferably in the range of 50 to 110 kg / m 3 .
- the thickness of the core layer of a foam part according to the invention for industrial applications, after separation of the foam skins may, for. B. in the range of 1 to 200 mm, in particular in the range of 5 to 100 and most preferably in the range of 10 to 70 mm
- the invention encompasses the use of the foam parts according to the invention as a part or component of parts, in particular as core materials for sandwich structures for motor vehicles, rail vehicles, aircraft, watercraft, spacecraft, machine parts, antennas, X-ray tables, speakers, pipes and blades of wind power plants.
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- Medicinal Chemistry (AREA)
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Abstract
L'invention concerne un procédé de fabrication d'une pièce en mousse à partir de poly(méth)acrylates réticulés, caractérisé par les étapes suivantes : a. polymérisation d'un mélange monomère polymérisable qui est composé principalement de monomères (méth)acrylates non réticulés, de réticulants et d'un système initiateur, par un procédé de polymérisation par coulée pour obtenir un prépolymérisat; b. chargement du prépolymérisat avec un gaz inerte comme agent d'expansion à une pression comprise entre 2 et 200 bars; c. abaissement de la pression et expansion du prépolymérisat à une température à laquelle le prépolymérisat chargé en agent d'expansion est expansible pour obtenir une pièce en mousse; c. stabilisation de la pièce en mousse par abaissement de la température. L'invention concerne par ailleurs la pièce en mousse et ses utilisations.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE200910027244 DE102009027244A1 (de) | 2009-06-26 | 2009-06-26 | Verfahren zur Herstellung eines Schaumstoffteils aus vernetzten Poly(meth)acrylaten sowie der Schaumstoff und dessen Verwendung |
DE102009027244.5 | 2009-06-26 |
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WO2010149441A1 true WO2010149441A1 (fr) | 2010-12-29 |
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PCT/EP2010/057072 WO2010149441A1 (fr) | 2009-06-26 | 2010-05-21 | Procédé de fabrication d'une pièce en mousse à partir de poly(méth)acrylates réticulés ainsi que ladite mousse et ses utilisations |
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WO (1) | WO2010149441A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180066078A1 (en) * | 2015-03-31 | 2018-03-08 | Evonik Roehm Gmbh | Production of a pmma foam using cross-linking agents, regulators and blowing agents |
US11155662B2 (en) | 2016-09-12 | 2021-10-26 | Evonik Operations Gmbh | Improving the properties in PMMA foams by using methacrylic amides |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US8692722B2 (en) | 2011-02-01 | 2014-04-08 | Phoenix Contact Development and Manufacturing, Inc. | Wireless field device or wireless field device adapter with removable antenna module |
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WO2007082304A2 (fr) * | 2006-01-12 | 2007-07-19 | Massachusetts Institute Of Technology | Élastomères biodégradables |
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DE3300526A1 (de) | 1983-01-10 | 1984-07-12 | Röhm GmbH, 6100 Darmstadt | Schlagzaehmodifizierungsmittel |
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2009
- 2009-06-26 DE DE200910027244 patent/DE102009027244A1/de not_active Withdrawn
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2010
- 2010-05-21 WO PCT/EP2010/057072 patent/WO2010149441A1/fr active Application Filing
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EP0874019A2 (fr) * | 1997-04-25 | 1998-10-28 | Röhm Gmbh | Procédé de préparation de mousses de polyméthacrylimide |
DE19909214A1 (de) * | 1999-03-03 | 2000-09-07 | Basf Ag | Wasserabsorbierende, schaumförmige, vernetzte Polymerisate mit verbesserter Verteilungswirkung, Verfahren zu ihrer Herstellung und ihre Verwendung |
US6207724B1 (en) * | 2000-01-24 | 2001-03-27 | The Procter & Gamble Company | Foam materials and high internal phase emulsions made using oxidatively stable emulsifiers |
WO2002012379A1 (fr) * | 2000-08-05 | 2002-02-14 | Zotefoams Plc | Procede de preparation de polymeres expanses reticules |
WO2002096635A1 (fr) * | 2001-05-25 | 2002-12-05 | Apache Products Company | Microspheres expansibles pour isolation mousse et procedes correspondants |
WO2007082304A2 (fr) * | 2006-01-12 | 2007-07-19 | Massachusetts Institute Of Technology | Élastomères biodégradables |
Cited By (3)
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US20180066078A1 (en) * | 2015-03-31 | 2018-03-08 | Evonik Roehm Gmbh | Production of a pmma foam using cross-linking agents, regulators and blowing agents |
US10954319B2 (en) * | 2015-03-31 | 2021-03-23 | Evonik Operations Gmbh | Production of a PMMA foam using cross-linking agents, regulators and blowing agents |
US11155662B2 (en) | 2016-09-12 | 2021-10-26 | Evonik Operations Gmbh | Improving the properties in PMMA foams by using methacrylic amides |
Also Published As
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DE102009027244A1 (de) | 2010-12-30 |
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