EP3673009A1 - Pei-partikelschäume für anwendungen im luftfahrt-interieur - Google Patents

Pei-partikelschäume für anwendungen im luftfahrt-interieur

Info

Publication number
EP3673009A1
EP3673009A1 EP18753207.2A EP18753207A EP3673009A1 EP 3673009 A1 EP3673009 A1 EP 3673009A1 EP 18753207 A EP18753207 A EP 18753207A EP 3673009 A1 EP3673009 A1 EP 3673009A1
Authority
EP
European Patent Office
Prior art keywords
particle foam
pei
foam
foamed
particle
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.)
Pending
Application number
EP18753207.2A
Other languages
German (de)
English (en)
French (fr)
Inventor
Christian Trassl
Denis HOLLEYN
Kay Bernhard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP3673009A1 publication Critical patent/EP3673009A1/de
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16Making expandable particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/10Making granules by moulding the material, i.e. treating it in the molten state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B21/04Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B7/04Interconnection of layers
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    • CCHEMISTRY; METALLURGY
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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    • C08J9/16Making expandable particles
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/228Forming foamed products
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/22After-treatment of expandable particles; Forming foamed products
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    • C08J9/232Forming foamed products by sintering expandable particles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J9/22After-treatment of expandable particles; Forming foamed products
    • C08J9/228Forming foamed products
    • C08J9/236Forming foamed products using binding agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29B9/00Making granules
    • B29B9/16Auxiliary treatment of granules
    • B29B2009/166Deforming granules to give a special form, e.g. spheroidizing, rounding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08PI, i.e. polyimides or derivatives thereof
    • B29K2079/085Thermoplastic polyimides, e.g. polyesterimides, PEI, i.e. polyetherimides, or polyamideimides; Derivatives thereof
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    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04Condition, form or state of moulded material or of the material to be shaped cellular or porous
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    • B32B2307/40Properties of the layers or laminate having particular optical properties
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    • CCHEMISTRY; METALLURGY
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2205/10Rigid foams
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Definitions

  • PEI particle foams for applications in the aviation interior are PEI particle foams for applications in the aviation interior
  • Polymeric foams based on polyetherimides (PEI) fulfill the aviation requirements of the aviation industry. Especially the requirements of the fire behavior, the media resistance and the mechanics make a big difference here
  • suitable polymer foams are produced as semi-finished products.
  • Post-processing to moldings is uneconomical in terms of time and material utilization, such as e.g. due to large amounts of cut waste.
  • the invention solves this problem by the fact that the material suitable in principle can be processed into particle foam moldings. These moldings can be produced without reworking in short cycle times and thus economically. Furthermore, this opens up new possibilities of functional integration, such as by direct foaming of inserts, etc., and in terms of creative freedom.
  • Suitable foams for installation in the aviation industry are well known. However, for the most part only foams of pure PMI (polymethacrylimide), PPSU (polyphenylene sulfones) or PES (polyethsulfones) are described. Also found in the literature but unsuitable from a toxicological point of view is also PI (polyarylimide). All these
  • PESU poly (oxy-1, 4-phenylsulfonyl-1, 4-phenyl)
  • DIAB Divinycell F
  • An economical method of avoiding cut-off in the manufacture of three-dimensional foam moldings is the use of bead foams rather than block foams. All of the prior art particulate foams have either disadvantages in use at high temperatures, or overall, and especially at these high temperatures, inadequate mechanical properties. In addition, very few foams are known that are not easy to inflame and Therefore, for example, in the interiors of road, rail or aircraft can be installed.
  • particle foams based on polypropylene (EPP), polystyrene (EPS), thermoplastic polyurethane elastomer (E-TPU) or PMI have inadequate flame retardancy, while all of them are inherently suitable
  • flame retarded polymers e.g. PES, PEI or PPSU according to the current state of the art can only be processed into block foams.
  • Composition for producing novel foams or composite materials which are, for example, a foam core with thermoplastic or crosslinked
  • Cover layers may be available for use in aircraft construction.
  • the resulting foams should have a good combination of applicability at high temperatures, good mechanical properties, in particular with respect to a sufficient elongation at break and for many applications in the field of vehicle and aircraft at least sufficient flame retardancy.
  • the foam should have a high resistance to various liquid, acidic, basic or hydrophobic liquids and to emulsions. Furthermore, from the composition to be developed by a variety of methods and with a wide range of three-dimensional shapes of the foam should be feasible and in the production of the final component as little or no waste as possible.
  • This composition according to the invention for producing foams is characterized in that it is is a particle foam based on polyetherimides (PEI).
  • PEI polyetherimides
  • the particle foam according to the invention has a glass transition temperature between 180 and 215 ° C. as the foamed material, and in which the average cell diameter of the particle foam is less than 2 mm, preferably less than 1 mm, more preferably less than 500 ⁇ m and very particularly preferably less than 250 ⁇ m.
  • the term cell describes a region in a foam which contains no matrix material but is at least partially enclosed by it.
  • Cells are also called pores.
  • these pores or cells are closed, which in turn means that the cell is completely enclosed by the matrix material of the foam.
  • a softer foam at least partially open cells are present.
  • a foam particle is understood according to the invention to mean the region in a particle foam which is defined by foaming a single unfoamed or prefoamed particle.
  • the boundary between the individual, interconnected foam particles can be easily recognized with the naked eye or determined under a light microscope. This is particularly applicable when the interfaces between two foam particles are clearly visible. Since this does not necessarily have to be the case, a simplified method is used according to the invention: for this purpose, a theoretical average diameter of a
  • an advantage of the present invention is that the volume fraction of the gusset between the individual foam particles is so small that it hardly comes into play in the volume measurement of the finished foam part.
  • These foam particles are preferably less than 1 cm in the finished foam, more preferably less than 0.7 cm.
  • Given glass transition temperatures are inventively - unless otherwise stated - measured by DSC (Differential Scanning Calometry). The skilled person knows that the DSC is only sufficiently meaningful if, after a first heating cycle up to a temperature which is at least 25 ° C above the highest glass transition or
  • the material sample is held for at least 2 min at this temperature. Thereafter, the mixture is again cooled to a temperature which is at least 20 ° C below the lowest glass transition or melting temperature to be determined, the cooling rate should be a maximum of 20 ° C / min, preferably a maximum of 10 ° C I min. After a further waiting time of a few minutes, the actual measurement takes place, in which the sample is heated to at least 20 ° C. above the highest melting or glass transition temperature at a heating rate of generally 10 ° C./min or less.
  • the composition according to the invention for producing the particle foam in a first alternative embodiment of the invention preferably consists of 80 to 99.5% by weight PEI. Furthermore, this composition has 0.5 to 10% by weight, preferably 1 to 9% by weight of a blowing agent. In addition, among other things 0 to 10 wt%, preferably 1 to 5 wt% additives may be included.
  • the additives may in particular be flame retardant additives, plasticizers, pigments, UV stabilizers, nucleating agents, impact modifiers, adhesion promoters, rheology modifiers, chain extenders, fibers and / or nanoparticles.
  • phosphorus compounds in particular phosphates, phosphines or phosphites are used.
  • Suitable UV stabilizers or UV absorbers are generally known to the person skilled in the art.
  • HALS compounds Tiuvine or triazoles.
  • the impact modifiers used are generally polymer particles comprising an elastomer or soft phase. These are often core (shell) shell particles, with an outer shell that is as a maximum weakly crosslinked and as a pure polymer would have an at least minimum miscibility with the PEI.
  • all known pigments can be used as pigments.
  • the influence on the foaming process - as with all other additives used in larger amounts of more than 0.1% by weight - should be investigated. This is feasible for the skilled person with relatively little effort.
  • Suitable plasticizers, rheology modifiers and chain extenders are generally known to the person skilled in the art from the production of films, membranes or molded parts from PEI or blends containing PEI and can accordingly be transferred to the preparation of a foam from the composition according to the invention with little effort.
  • the optionally added fibers are typically known fiber materials that can be added to a polymer composition.
  • the fibers are PEI, PES, PPSU or blend fibers, the latter of a selection of the polymers mentioned.
  • the nanoparticles which can be present, for example, as tubes, flakes, rods, spheres or in other known forms, are generally inorganic materials. These can take on different functions in the finished foam. Thus, these particles partially act as nucleating agents during foaming. Furthermore, the particles can influence the mechanical properties as well as the (gas) diffusion properties of the foam. Furthermore, the particles additionally contribute to the low flammability.
  • phase-separating polymers can also be added as nucleating agents.
  • the polymers described are separated from the others in the consideration of the composition
  • Nucleating agents as these primarily affect the mechanical properties of the foam, the melt viscosity of the composition and thus the
  • the additives may optionally also contain up to 9% by weight of a further polymer component for adjusting the physical properties.
  • the additional polymers may be, for example, polyamides, polyolefins, in particular PP, polyesters, in particular PET, sulfur-based polymers, such as, for example, PSU, PPSU, PES or poly (meth) acrylimide.
  • blowing agent is relatively free and determined for the skilled person in particular by the chosen Shuumungsmethode, the solubility in the polymer and the foaming temperature.
  • alcohol such as e.g. Isopranol or butanol
  • ketones such as acetone or
  • Methyl ethyl ketone alkanes, such as iso- or n-butane, pentane, hexane, heptane or octane, alkenes, such as pentene, hexene, heptene or octene, CO2, N2, water, ethers, such as diethyl ether, aldehydes , such as Formaldehyde or propanal, fluorinated (chlorinated) hydrocarbons, chemical blowing agents or mixtures of several of these substances.
  • alkanes such as iso- or n-butane
  • pentane hexane
  • heptane or octane alkenes
  • alkenes such as pentene, hexene, heptene or octene
  • CO2, N2 water
  • ethers such as diethyl ether
  • aldehydes such as
  • the chemical blowing agents are less or non-volatile substances that are chemically decomposed under the foaming conditions and thereby the actual
  • Form blowing agent A very simple example of this is tert-butanol, which is under
  • Foaming conditions isobutene and water forms.
  • Further examples are NaHCCh, citric acid or their derivatives, azodicarbonamide (ADC) or compounds thereof,
  • TSH Toluenesulfonylhydrazine
  • OBSH oxybis (benzosulfohydrozide)
  • 5-phenyltetrazole 5-PT
  • the particle foam of the invention has a tensile strength according to IS01926 greater than 0.5 MPa, an elongation at break according to IS01926 between 8 and 12%, a shear modulus according to ASTM C273 at room temperature greater than 8 MPa, a shear strength according to ASTM C273 at
  • Aircraft industry in particular for use in the interior of an aircraft important fire safety regulations or fire properties applicable to FAR 25.852 is applicable.
  • Characteristics such that they differ in a surface and an axis perpendicular to this surface. Depending on the specific application, isotropic mechanical properties can be quite advantageous, especially if pressure loads occur uniformly from different directions.
  • the foams according to the invention preferably have a degree of foaming which constitutes a reduction in density compared with the unfoamed material of between 1 and 98%, preferably between 50 and 97%, particularly preferably between 70 and 95%.
  • the foam has a density between 20 and 1000 kg / m 3 , preferably 40 and 250 kg / m 3, particularly preferably between 50 and 150 kg / m 3 .
  • a composition consisting of 80 to 99.5% by weight of PEI, 0.5 to 10% by weight of blowing agent and 0 to 10% by weight of additives is processed by means of an extruder with perforated plate to a foamed or foamable granules.
  • the temperatures between feed zone and screw tip are preferably in a range between 320 and 400 ° C. Furthermore, there is usually no uniform temperature over this distance, but, for example, a gradient with increasing temperature in the conveying direction of the polymer melt.
  • the temperature of the perforated plate is between 250 and 350 ° C and the melt temperature at the exit through the perforated plate between 230 and 360 ° C.
  • the loading with the propellant takes place in the extruder.
  • the granules then foam on exiting the perforated plate when the pressure in the underwater granulation is less than the expansion force of the propellant.
  • the granulate thus foamed is then preferably further processed into a particle foam.
  • Extruders are directed into an underwater granulator. This is designed so with respect to a combination of temperature and pressure that foaming is prevented. This procedure results in a granulate laden with propellant, which can later be foamed by renewed energy supply to the desired density and / or can be further processed under optional shaping to form a particle foam workpiece.
  • the energy input necessary for prefouching can be achieved by means of contact heat, e.g. in a convection oven or
  • Composition consisting of 90 to 100% by weight of PEI and 0 to 10% by weight of additives by means of an extruder with perforated plate also initially processed into granules, but not loaded with a propellant.
  • the temperatures which are again not necessarily uniform, between intake zone and screw tip lie in a range between 320 and 400 ° C.
  • the temperature of the perforated plate between 250 and 350 ° C and the melt temperature at the exit through the perforated plate between 230 and 360 ° C.
  • the granules are then loaded in an autoclave with a propellant so that it contains between 0.5 and 10 wt% propellant.
  • the propellant loaded granules can then be foamed by relaxing and / or by heating to a temperature of about 200 ° C to a particle foam.
  • the skilled person is fundamentally familiar with various methods for foaming polymer compositions which are applicable to the present composition, in particular with regard to methods for thermoplastic foams.
  • the composition can be foamed at a temperature between 150 and 250 ° C and a pressure between 0, 1 and 2 bar.
  • the actual foaming takes place, if not following extrusion, at a temperature between 180 and 230 ° C in a normal pressure atmosphere.
  • a composition still without propellant, in an autoclave at a temperature e.g. between 20 and 120 ° C and a pressure e.g. between 30 and 100 bar applied to the propellant and then foamed by lowering the pressure and raising the temperature to the foaming temperature in the autoclave.
  • a pressure e.g. between 30 and 100 bar applied to the propellant and then foamed by lowering the pressure and raising the temperature to the foaming temperature in the autoclave.
  • Welded means that by heating the components, a material bond or an adhesion between the materials, e.g. by partially filling open pores at the
  • Foam surface with cover material arises.
  • the cover material can be wood, metals, decorative films, composite materials, prepregs or other known materials.
  • the produced particle foam can alternatively in the presence of a
  • Covering material are foamed so that it is connected to this by means of gluing or welding.
  • the PEI can alternatively also be added on leaving the extruder in an optionally heated mold, optionally containing cover materials. It is foamed with shaping to form a particle foam or a composite material. Alternatively, upon exiting the extruder, the composition may be passed into a foam spray device. In this device is then foamed directly under shaping.
  • the particle foams or composite materials can be seen during the foaming with inserts and / or channels can be installed in the particle foam.
  • the foams according to the invention or the foams produced by the process according to the invention are used in the construction of spacecraft or aircraft, especially in their interior or exterior use. This may include the particle foams produced by the process of the invention or not, as well as the composite materials realized therefrom. In particular, due to the low flammability foams of the invention can be installed in the interior of these vehicles.
  • the pure PEI particle foams are particularly suitable for being installed in the interior of an aircraft.
  • aircraft also include helicopters or even spacecraft. Examples of the installation in the interior of such an aircraft are, for example, the fold-out trays on the seat back of a passenger machine, the filling of a seat or a partition, and, for example, in internal doors.
  • particle foams based on a blend containing PEI are also suitable for incorporation in the exterior of an aircraft.
  • Outside means not only as a filling in the outer skin of an aircraft, but in particular in an aircraft nose, in the rear area, in the wings, in the outer doors, in the oars or in rotor blades.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Molding Of Porous Articles (AREA)
EP18753207.2A 2017-08-24 2018-08-20 Pei-partikelschäume für anwendungen im luftfahrt-interieur Pending EP3673009A1 (de)

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CA3073778A1 (en) 2019-02-28
SG11202001473WA (en) 2020-03-30
KR102628067B1 (ko) 2024-01-23
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WO2019038213A1 (de) 2019-02-28
MX2020001993A (es) 2020-09-25
AU2018321107A1 (en) 2020-04-09
ZA202001702B (en) 2021-05-26
RU2020111351A3 (ko) 2021-09-28
IL272841A (en) 2020-04-30
US11814499B2 (en) 2023-11-14
KR20200044073A (ko) 2020-04-28
AU2018321107C1 (en) 2024-08-15
AU2018321107B2 (en) 2024-05-16
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US20200207939A1 (en) 2020-07-02

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