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WO2017100397A1 - Fabrication additive d'articles utiles pour aéronef - Google Patents

Fabrication additive d'articles utiles pour aéronef Download PDF

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Publication number
WO2017100397A1
WO2017100397A1 PCT/US2016/065516 US2016065516W WO2017100397A1 WO 2017100397 A1 WO2017100397 A1 WO 2017100397A1 US 2016065516 W US2016065516 W US 2016065516W WO 2017100397 A1 WO2017100397 A1 WO 2017100397A1
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WIPO (PCT)
Prior art keywords
article
thermoplastic polymer
layers
brominated
foregoing
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PCT/US2016/065516
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English (en)
Inventor
Paul Dean Sybert
Yuanqing He
Robert Russell Gallucci
Malvika BIHARI
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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Publication of WO2017100397A1 publication Critical patent/WO2017100397A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing

Definitions

  • additive manufacturing also known in the art as "three-dimensional or "3D” printing
  • additive manufacturing is a process for the manufacture of three-dimensional objects by formation of multiple fused layers. Because multiple layers, for example greater than fifty (or more), are formed in AM processes, interlayer adhesion is an important consideration for both process parameter and final product specifications. Accordingly, there remains a need for AM methods that allow for better interlayer adhesion, especially when used in aircraft useful in aircraft or other passenger conveyances.
  • One embodiment is a method of making an article useful in aircraft or other passenger conveyances, the method comprising: melt extruding a plurality of layers comprising a thermoplastic polymer composition in a preset pattern; and fusing the plurality of layers to provide the article; wherein the thermoplastic polymer composition comprises a combination of a polycarbonate polymer or copolymer, a polyetherimide polymer or copolymer, a
  • thermoplastic polymers or copolymer, or a combination comprising at least one of the foregoing thermoplastic polymers, and a non-brominated and non-chlorinated organic phosphorus-containing additive that will lower the Tg of the thermoplastic polymer from 5 to 100 degrees C and wherein the article has a 2 minute integrated heat release rate of less than or equal to 65 kilowatt-minutes per square meter (kW-min/m 2 ) and a peak heat release rate of less than 65 kilowatts per square meter (kW/m 2 ) as measured using the method of FAR F25.4, in accordance with Federal Aviation Regulation FAR 25.853 (d).
  • thermoplastic polymer composition comprises a combination of a polycarbonate polymer or copolymer, a polyetherimide polymer or copolymer, a polyarylethersulfone polymer or copolymer, or a combination comprising at least one of the foregoing thermoplastic polymers, and a non-brominated and non-chlorinated organic phosphorus-containing that will lower the Tg of the thermoplastic polymer and wherein the article has a 2 minute integrated heat release rate of less than or equal to 65 kilowatt-minutes per square meter (kW-min/m2) and a peak heat release rate of less than 65 kilowatts per square meter (kW/m 2 ) as measured using the method of FAR F25.4, in accordance with Federal
  • thermoplastic engineering blended articles by additive manufacturing processes such as by fused deposition modeling (FDM) for use in aircraft.
  • FDM fused deposition modeling
  • the resulting polymeric compositions have a lower glass transition temperature (Tg) are achieved which would lead to AM parts with better physical properties because the fused AM layers can have better interfacial adhesion as a result of the better flow and a longer time in the molten state.
  • these phosphate blends comply with Federal Aviation Regulation (FAR) rating for aircraft interiors and EN-45545 ratings railway and railway applications and have excellent PC-PE-SI and vertical burn properties.
  • a plurality of layers is formed in a preset pattern by an additive manufacturing process.
  • "Plurality" as used in the context of additive manufacturing includes 20 or more layers.
  • the maximum number of layers can vary greatly, determined, for example, by considerations such as the size of the article being manufactured, the technique used, the capabilities of the equipment used, and the level of detail desired in the final article. For example, 20 to 100,000 layers can be formed, or 50 to 50,000 layers can be formed.
  • layer is a term of convenience that includes any shape, regular or irregular, having at least a predetermined thickness.
  • the size and configuration two dimensions are predetermined, and on some embodiments, the size and shape of all three dimensions of the layer is predetermined.
  • the thickness of each layer can vary widely depending on the additive manufacturing method. In some embodiments the thickness of each layer as formed differs from a previous or subsequent layer. In some embodiments, the thickness of each layer is the same. In some embodiments the thickness of each layer as formed is 0.5 millimeters (mm) to 5 mm. In other embodiments, the article is made from a
  • the monofilament can comprise an aromatic phosphate modified thermoplastic polymer with a diameter of from 0.1 to 5.0 mm.
  • the preset pattern can be determined from a three-dimensional digital representation of the desired article as is known in the art and described in further detail below.
  • thermoplastic material that is fusible to the next adjacent layer.
  • the plurality of layers in the predetermined pattern are fused to provide the article. Any method effective to fuse the plurality of layers during additive manufacturing can be used. In some embodiments, the fusing occurs during formation of each of the layers. In some embodiments the fusing occurs while subsequent layers are formed, or after all layers are formed.
  • an additive manufacturing technique known generally as material extrusion can be used.
  • material extrusion an article can be formed by dispensing a flowable material ("the build material") in a layer-by-layer manner and fusing the layers.
  • the flowable build material can be rendered flowable by dissolving or suspending the material in a solvent. In other embodiments, the flowable material can be rendered flowable by melting. In other embodiments, a flowable prepolymer
  • composition that can be crosslinked or otherwise reacted to form a solid can be used. Fusing can be by removal of the solvent, cooling of the melted material, or reaction of the prepolymer composition.
  • an article can be formed from a three-dimensional digital representation of the article by depositing the flowable material as one or more roads on a substrate in an x-y plane to form the layer.
  • the position of the dispenser e.g., a nozzle
  • the dispensed material is thus also referred to as a "modeling material” as well as a "build material.”
  • a support material as is known in the art can optionally be used to form a support structure.
  • the build material and the support material can be selectively dispensed during manufacture of the article to provide the article and a support structure.
  • the support material can be present in the form of a support structure, for example, a scaffolding that can be mechanically removed or washed away when the layering process is completed to the desired degree.
  • An exemplary material extrusion additive manufacturing system includes a build chamber and a supply source for the thermoplastic material.
  • the build chamber includes a build platform, a gantry, and a dispenser for dispensing the thermoplastic material, for example an extrusion head.
  • the build platform is a platform on which the article is built, and desirably moves along a vertical z-axis based on signals provided from a computer-operated controller.
  • the gantry is a guide rail system that can be configured to move the dispenser in a horizontal x-y plane within the build chamber, for example based on signals provided from a controller.
  • the horizontal x-y plane is a plane defined by an x-axis and a y-axis where the x-axis, the y-axis, and the z-axis are orthogonal to each other.
  • the platform can be configured to move in the horizontal x-y plane and the extrusion head can be configured to move along the z-axis.
  • Other similar arrangements can also be used such that one or both of the platform and extrusion head are moveable relative to each other.
  • the build platform can be isolated or exposed to atmospheric conditions.
  • both the build structure and the support structure of the article formed can include a fused expandable layer.
  • the build structured includes a fused expandable layer and the support material does not include an expandable layer.
  • the build structure does not include an expandable layer and the support structure does include a fused expandable layer.
  • the lower density of the expanded layer can allow for the support material to be easily or more easily broken off than the non-expanded layer, and re-used or discarded.
  • the support structure can be made purposely breakable, to facilitate breakage where desired.
  • the support material can have an inherently lower tensile or impact strength than the build material.
  • the shape of the support structure can be designed to increase the breakability of the support structure relative to the build structure.
  • the build material can be made from a round print nozzle or round extrusion head.
  • a round shape as used herein means any cross-sectional shape that is enclosed by one or more curved lines.
  • a round shape includes circles, ovals, ellipses, and the like, as well as shapes having an irregular cross-sectional shape.
  • Three dimensional articles formed from round shaped layers of build material can possess strong structural strength.
  • the support material for the articles can be made from a non-round print nozzle or non-round extrusion head.
  • a non-round shape means any cross- sectional shape enclosed by at least one straight line, optionally together with one or more curved lines.
  • a non-round shape can include squares, rectangles, ribbons, horseshoes, stars, T head shapes, X shapes, chevrons, and the like. These non-round shapes can render the support material weaker, brittle and with lower strength than round shaped build material.
  • the above material extrusion techniques include techniques such as fused deposition modeling and fused filament fabrication as well as others as described in ASTM F2792-12a.
  • fused material extrusion techniques an article can be produced by heating a thermoplastic material to a flowable state that can be deposited to form a layer.
  • the layer can have a predetermined shape in the x-y axis and a predetermined thickness in the z-axis.
  • the flowable material can be deposited as roads as described above, or through a die to provide a specific profile.
  • the layer cools and solidifies as it is deposited.
  • a subsequent layer of melted thermoplastic material fuses to the previously deposited layer, and solidifies upon a drop in temperature. Extrusion of multiple subsequent layers builds the desired shape.
  • At least one layer of an article is formed by melt deposition, and in other embodiments, more than 10, or more than 20, or more than 50 of the layers of an article are formed by melt deposition, up to and including all of the layers of an article being formed by melt deposition.
  • thermoplastic polymer is supplied in a melted form to the dispenser.
  • the dispenser can be configured as an extrusion head.
  • the extrusion head can deposit the thermoplastic composition as an extruded material strand to build the article.
  • the thermoplastic material can be extruded at a temperature of 200 to 450°C. In some embodiments the thermoplastic material can be extruded at a temperature of 300 to 415°C.
  • the layers can be deposited at a build temperature (the temperature of deposition of the thermoplastic extruded material) that is 50 to 200°C lower than the extrusion temperature. For example, the build temperature can be 15 to 250°C. In some embodiments the thermoplastic material is extruded at a temperature of 200 to 450°C, or 300 to 415°C, and the build temperature is maintained at ambient temperature.
  • Tg-lowering additive can be incorporated into a melt of the thermoplastic material, then the melt formed into the desired shape and cooled.
  • a Tg-lowering additive can be added directly to the melt used in the additive manufacturing process, or pre-incorporated or blended into the thermoplastic polymer material and the mixture can be melted together during the additive manufacturing process.
  • the Tg lowering additive must not compromise the rigorous FAR flame resistance of the monofilament manufactured article.
  • thermoplastic polymers examples include
  • polyarylsulf ones polycarbonates (including polycarbonate homopolymers and polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester- siloxanes), polyetherimides (including homopolymers and copolymers such as polyetherimide- siloxane copolymers), or a combination comprising at least one of the foregoing thermoplastic polymers.
  • homopolymers and copolymers are especially useful in a wide variety of articles, have good processability, and are recyclable.
  • Exemplary polycarbonates are described, for example, in US 7,790,292 B2, US 2007/0066737 Al, WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923.
  • Polycarbonates are generally manufactured from bisphenol compounds such as 2,2-bis(4- hydroxyphenyl) propane (“bisphenol- A” or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclohexane, or 1 , 1 -bis(4-hydroxy-3-methylphenyl)-3 ,3 ,5- trimethylcyclohexane, or a combination comprising at least one of the foregoing bisphenol compounds can also be used.
  • the polycarbonate is a homopolymer derived from BPA or a copolymer derived from BPA and another bisphenol or dihydroxy aromatic compound such as resorcinol.
  • polycarbonate copolymers include poly(aliphatic ester-carbonate) poly(siloxane-carbonate), and polycarbonate-ester-siloxanes).
  • specific polycarbonates that can be used include poly(ester-carbonate-siloxane)s comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units, for example blocks containing 5 to 50 dimethylsiloxane units, such as those commercially available under the trade name PC-PE-SI from the Innovative Plastics division of SABIC or those described in claim 1 of US Patent No. 7,790,292, which is incorporated herein in its entirety.
  • Polyetherimides comprise more than 1, for example 10 to 1000, or 10 to 500, struc (1)
  • each R is the same or different, and is a substituted or unsubstituted divalent organic group, such as a C6-20 aromatic hydrocarbon group or a halogenated derivative thereof, a straight or branched chain C2-20 alkylene group or a halogenated derivative thereof, a C3-8 cycloalkylene group or halogenated derivative thereof, in particular a divalent group of formula (2):
  • Ql is -0-, -S-, -C(O)-, -S02-, -SO-, -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups), or -(C6H10)z- wherein z is an integer from 1 to 4.
  • R is m-phenylene, p-phenylene, or a diaryl sulfone.
  • T is -O- or a group of the formula -0-Z-O- wherein the divalent bonds of the -O- or the -0-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions.
  • the group Z in -0-Z-O- of formula (1) is also a substituted or unsubstituted divalent organic group, and can be an aromatic C6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Cl-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, provided that the valence of Z is not exceeded.
  • Exemplary groups Z include groups derived from a dihydroxy compound of formula
  • Ra and Rb can be the same or different and are a halogen atom or a monovalent Cl-6 alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and Xa is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para
  • the bridging group Xa can be a single bond, -0-, -S-, -S(0 , -S(0)2-, -C(O)-, or a Cl-18 organic bridging group.
  • the Cl-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the Cl-18 organic group can be disposed such that the C6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Cl-18 organic bridging group. is a divalent group of formula (3a):
  • Q is -0-, -S-, -C(O)-, -S02-, -SO-, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group).
  • Z is a derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.
  • R is m-phenylene or p-phenylene and T is -O- Z-0 wherein Z is a divalent group of formula (3a).
  • R is m-phenylene or p- phenylene and T is -O-Z-0 wherein Z is a divalent group of formula (3a) and Q is 2,2- isopropylidene.
  • the polyetherimide can be a copolymer, for example, a polyetherimide sulfone copolymer comprising structural units of formula (1) wherein at least 50 mole% of the R groups are of formula (2) wherein Ql is -S02- and the remaining R groups are independently p-phenylene or m-phenylene or a combination comprising at least one of the foregoing; and Z is 2,2'-(4-phenylene)isopropylidene.
  • the polyetherimide optionally comprises additional structural imide units, for example imide units of formula (4):
  • R is as described in formula (1) and W is a linker of the formulas
  • additional structural imide units can be present in amounts from 0 to 10 mole % of the total number of units, specifically 0 to 5 mole %, more specifically 0 to 2 mole %. In an embodiment no additional imide units are present in the polyetherimide.
  • polyetherimide can be prepared by any of the methods well known to those skilled in the art, inc bis(ether anhydride) of formula (5):
  • Copolymers of the polyetherimides can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (4) and a different bis(anhydride), for example a bis(anhydride) wherein T does not contain an ether functionality, for example T is a sulfone.
  • bis (anhydride) s include 3,3-bis[4-(3,4- dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4- dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(2,3- dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)dip
  • organic diamines examples include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylene tetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
  • the organic diamine is m-phenylenediamine, p-phenylenediamine, sulfonyl dianiline, or a combination comprising one or more of the foregoing.
  • the polyetherimides can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370°C, using a 6.7 kilogram (kg) weight.
  • the polyetherimide polymer has a weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole (Dalton), as measured by gel permeation chromatography, using polystyrene standards.
  • Mw weight average molecular weight
  • polyetherimide has an Mw of 10,000 to 80,000 Daltons. Such polyetherimide polymers typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in m-cresol at 25°C.
  • thermoplastic composition can also comprise a poly(siloxane-etherimide) copolymer comprising polyetherimide units of formula (1) and siloxane blocks of formula (7):
  • each R' is independently a Cl-13 monovalent hydrocarbyl group.
  • each R' can independently be a Cl-13 alkyl group, Cl-13 alkoxy group, C2-13 alkenyl group, C2-13 alkenyloxy group, C3-6 cycloalkyl group, C3-6 cycloalkoxy group, C6-14 aryl group, C6-10 aryloxy group, C7-13 arylalkyl group, C7-13 arylalkoxy group, C7-13 alkylaryl group, or C7-13 alkylaryloxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination comprising at least one of the foregoing.
  • the polysiloxane blocks comprises R' groups that have minimal hydrocarbon content.
  • an R' group with a minimal hydrocarbon content is a methyl group.
  • the poly(siloxane-etherimide) can be a block or graft copolymer.
  • Block poly(siloxane-etherimide) copolymers comprise etherimide units and siloxane blocks in the polymer backbone.
  • the etherimide units and the siloxane blocks and the can be present in random order, as blocks (i.e., AABB), alternating (i.e., ABAB), or a combination thereof.
  • Graft poly(siloxane-etherimide) copolymers are non- linear copolymers comprising the siloxane blocks connected to linear or branched polymer backbone comprising etherimide blocks.
  • the poly (siloxane-etherimide)s can be formed by polymerization of an aromatic bis anhydride (4) and a diamine component comprising an organic diamine (6) as described above or mixture of diamines, and a polysiloxane diamine of formula (8):
  • R4 is each independently a C2-C20 hydrocarbon, in particular a C2-C20 arylene, alkylene, or arylenealkylene group.
  • R4 is a C2-C20 alkyl group, specifically a C2-C20 alkyl group such as propylene
  • E has an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15, or 15 to 40.
  • the diamine component can contain 10 to 90 mole percent (mol %), or 20 to 50 mol%, or 25 to 40 mol% of polysiloxane diamine (7) and 10 to 90 mol%, or 50 to 80 mol%, or 60 to 75 mol% of diamine (5), for example as described in US Patent 4,404,350.
  • the diamine components can be physically mixed prior to reaction with the bisanhydride(s), thus forming a substantially random copolymer.
  • block or alternating copolymers can be formed by selective reaction of (5) and (7) with aromatic dianhydrides (20), to make polyimide blocks that are subsequently reacted together.
  • the poly(siloxane-imide) copolymer can be a block, random, or graft copolymer.
  • poly(siloxane-etherimide) examples of specific poly(siloxane-etherimide) are described in US Pat. Nos. 4,404,350, 4,808,686 and 4,690,997.
  • the poly(siloxane-etherimide) has units of formula (9):
  • R' and E of the siloxane are as in formula (6), the R and Z of the imide are as in formula (1), R4 is the same as R4 as in formula (8), and n is an integer from 5 to 100.
  • the R of the etherimide is a phenylene
  • Z is a residue of bisphenol A
  • R4 is n- propylene
  • E is 2 to 50, 5, to 30, or 10 to 40
  • n is 5 to 100
  • each R' of the siloxane is methyl.
  • poly(siloxane-etherimide) depends on the desired properties, and are selected using the guidelines provided herein.
  • the block or graft poly(siloxane- etherimide) copolymer is selected to have a certain average value of E, and is selected and used in amount effective to provide the desired wt% of polysiloxane units in the composition.
  • the poly(siloxane-etherimide) comprises 10 to 50 wt%, 10 to 40 wt%, or 20 to 35 wt% polysiloxane units, based on the total weight of the poly(siloxane-etherimide).
  • alkyl includes branched or straight chain, unsaturated aliphatic Cl-30 hydrocarbon groups e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, n- and s-hexyl, n-and s-heptyl, and, n- and s-octyl.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3-)).
  • Cycloalkylene means a divalent cyclic alkylene group, -CnH2n-x, wherein x represents the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent group having one or more rings and one or more carbon-carbon double bond in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
  • aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as to phenyl, tropone, indanyl, or naphthyl.
  • halo means a group or compound including one more of a fluoro, chloro, bromo, iodo, and astatino substituent.
  • a combination of different halo groups e.g., bromo and fluoro
  • chloro groups e.g., bromo and fluoro
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, or P.
  • substituents independently selected from, a Cl-9 alkoxy, a Cl-9 haloalkoxy,
  • heterocycloalkyl and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom's normal valence is not exceeded.
  • Polyarylethersulfones include polyphenylethersulfone which is an amorphous plastic. This material combines a high melting temperature with quite a low moisture absorption. Furthermore, it has good impact strength and chemical resistance. [0045] The thermoplastic polysulfones, polyethersulfones and polyphenylene ether sulfones polyethersulfones can be prepared as described in U.S. Patent Nos. 3,634,355,
  • Polyaryl ether sulfones also referred to as polysulfones, polyether sulfones and polyphenylene ether sulfones are linear thermoplastic polymers that possess a number of attractive features such as high temperature resistance, good electrical properties, and good hydrolytic stability.
  • a variety of polyaryl ether sulfones are commercially available, including the polycondensation product of dihydroxy diphenyl sulfone with dichloro diphenyl sulfone and known as polyether sulfone (PES), and the polymer of bisphenol-A and dichloro diphenyl sulfone known in the art as polysulfone (PSu or PSF).
  • polyaryl ether sulfones are the polybiphenyl ether sulfones, available from Solvay Inc. under the trade mark of RADEL R. This polymer can be described as the product of the polycondensation of biphenol with 4,4'- dichlorodiphenyl sulfone and also is known and described in the art, for example, in Canadian Patent No. 847,963, which is incorporated by reference herein in its entirety.
  • Polysulfones are sold by Solvay Co. under the UDEL trade name.
  • Polyethersulfones are sold by Solvay under the RADEL A trade names and by BASF Co, as ULTRASON E.
  • the carbonate method in which at least one dihydric phenol and at least one dihalobenzenoid compound are heated, for example, with sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate is also disclosed in the art, for example in U.S. Patent No. 4, 176,222, which is incorporated by reference herein in its entirety.
  • polybiphenyl ether sulfone, PSu and PBS polymer components can be prepared by any of the variety of methods known in the art for the preparation of polyaryl ether polymers.
  • the molecular weight of the polysulfone as indicated by reduced viscosity data in an appropriate solvent such as methylene chloride, chloroform, N-methylpyrrolidone or the like, will be at least 0.3 dl/ g, preferably at least 0.4 dl/ g and, typically, will not exceed about 1.5 dV g. In some instances the polysulfone weight average molecular weight can vary from 10,000 to 100,000. Polysulfones can have glass transition temperatures from 180 to 250°C in some instances.
  • PBS copolymers for example comprising bisphenol A (BPA) moieties, other bisphenols and diphenyl ether sulfone moieties in molar ratios other than 1:1, can be used.
  • BPA bisphenol A
  • aromatic phosphates include, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,
  • Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of the formulas below:
  • Di- or polyfunctional aromatic phosphorus-containing compounds of this type include resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, respectively, their oligomeric and polymeric counterparts, and the like.
  • the amount of Tg-lowering additive can vary from wherein the amount of Tg-lowering additive is from 0.5% to 15 %, from 1% to 12%, or from 2% to 10% or any range within 1% to 30%, by weight, based on the weight of the thermoplastic polymer.
  • the thermoplastic polymer composition can include various other additives ordinarily incorporated into polymer compositions of this type, with the proviso that any additives is selected so as to not significantly adversely affect the desired properties of the thermoplastic composition, in particular the adhesion properties.
  • additives can be mixed at a suitable time during the mixing of the components for forming the composition.
  • Additives include nucleating agents, fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, , lubricants, mold release agents, surfactants, antistatic agents, colorants such as titanium dioxide, carbon black, and organic dyes, surface effect additives, radiation stabilizers, flame retardants, and anti-drip agents.
  • a combination of additives can be used, for example a combination of a heat stabilizer and ultraviolet light stabilizer.
  • the additives are used in the amounts generally known to be effective.
  • the total amount of the additives can be 0.01 to 5 wt.%, based on the total weight of the thermoplastic material.
  • thermoplastic composition and articles comprising the thermoplastic composition can exhibit at least one of the following desirable properties: a 2 minute integrated heat release rate of less than or equal to 65 kilowatt-minutes per square meter (kW-min/m 2 ), specifically less than or equal to 55 kW-min/m 2 , and a peak heat release rate of less than 65 kilowatts per square meter (kW/m 2 ), specifically less than or equal to 55 kW/m 2 as measured using the method of FAR F25.4, in accordance with Federal Aviation Regulation FAR 25.853 (d).
  • the article will be used in the interior of an aircraft or in construction of other passenger conveyances.
  • Such conveyances can be private or commercial conveyances and can be regulated by various governmental regulations concerning passenger safety in the event of a fire.
  • passenger conveyances include airplanes, helicopters, trains, commuter trains, busses, ships, excursion tour vehicles, tram cars, trolley cars, mobile homes, sleep-in recreation vehicles and the like.
  • Sample preparation Seven formulations were prepared using the raw material shown in Table 1 in the weight percentages shown in Table 2. The useful range of each ingredient is shown in Table 1.
  • Table 1 The polymers used in this study are described in Table 1. Examples of formulation that are useful for this invention are shown in Table 2 (Examples PC-PE-SiPC-PE-SI with Sol DP, PC-PE-SiPC-PE-SI with BPADP, PEI Blend with Sol-DP, and PPSU w Sol DP). Table 2 also shows comparative examples (PC-PE-SiPC-PE-SI, PEI blend, and PPSU).
  • Extrusions of the blends listed in Table 2 were carried out on a WERNER & PFLEIDERER 30 mm co-rotating twin screw extruder.
  • the powder blends were feed in the feed throat into the line before the Zone 1.
  • a vacuum vent is attached to the line and at Zone 5 a liquid injection system is attached via which the liquid flame retardants (BPADP) were injected.
  • BPADP liquid flame retardants
  • Typical temperature profile and processing conditions employed are shown in Table 3 below. All solid raw materials were pre-blended in a super blender and then fed into the extruder. All the solid components were fed from the main feed throat from upper stream. Table 3: Typical extrusion conditions (set value)
  • Table 4 depicts the molding conditions to mold strips of 5 x 0.5 x 0.04 inches (127 x 12.7 x 1 mm). All the samples could be molded successfully except the PPSU sample. PPSU sample could not fill in the 1mm strip tool due to very high melt viscosity. However with addition of Sol-DP, the sample (PPSU with Sol-DP) showed better flowability to the 1mm strip tool.
  • Sample strips of 5 x 0.5 x 0.04 inches (127 x 12.7 x 1 mm) were molded. Two such strips were stacked one on top of the other with 0.5 inch overlap. The samples were then sandwiched between quarter inch thick metal bars and placed in the oven at optimum temperature for appropriate time. A clip was used to clamp the 2 metal bars to ensure good contact between sample strips. The samples were then taken out and the strips were subjected to lap shear test using an Instron mechanical tester at a temperature of 23 °C and testing speed of 50 mm/min. Comparisons were made among various samples and depending on the decreasing order of force required to peel them apart and observing the sample failure mode, the type of break was classified as cohesive failure, adhesive failure and no breaks or yield and draw. A cohesive failure is defined as any failure or break away from the bonded surface. An adhesive failure is defined as failure at the bonded interface.
  • Type I Adhesive failure
  • Type II Cohesive failure
  • Type III No failure
  • Table 5 and 6 shows the results of the lap shear test for samples prepared under 2 types of structures: two layers and sandwich structure.
  • the aromatic organophosphorus such as BPADP and Sol-DP here can provide a plasticized effect in the blends. It can be seen from the data that the materials containing BPADP or Sol-DP shows cohesive failure for both the conditions tested thus exhibiting better interlayer adhesion. The control sample either does not stick or undergoes adhesive failure under the two conditions.
  • Table 7 shows the decreasing Tg and increasing MVR of the materials with addition of BPADP or Sol-DP.
  • Embodiment 1 A method of making an article useful in aircraft or other passenger conveyance interiors, the method comprising: melt extruding a plurality of layers comprising a thermoplastic polymer composition in a preset pattern; and fusing the plurality of layers to provide the article; wherein the thermoplastic polymer composition comprises a polycarbonate polymer or copolymer, a polyetherimide polymer or copolymer, a polyarylethersulfone polymer or copolymer, or a combination comprising at least one of the foregoing thermoplastic polymers and a non-brominated and non-chlorinated organic phosphorus-containing additive that will lower the Tg of the thermoplastic polymer from 5 to 100 degrees C and wherein the article has a 2 minute integrated heat release rate of less than or equal to 65 kilowatt-minutes per square meter (kW-min/m2) and a peak heat release rate of less than 65 kilowatts per square meter (kW/m2) as measured using the method
  • Embodiment 2 The method of Embodiment 1, wherein the thermoplastic polymer is a polycarbonate polymer or copolymer or a combination comprising at least one of the foregoing thermoplastic polymers and, optionally, wherein the article is made from layers built from a monofilament having a diameter from 0.1 to 5.0 mm.
  • the thermoplastic polymer is a polycarbonate polymer or copolymer or a combination comprising at least one of the foregoing thermoplastic polymers and, optionally, wherein the article is made from layers built from a monofilament having a diameter from 0.1 to 5.0 mm.
  • Embodiment 3 The method of Embodiment 1, wherein the thermoplastic polymer comprise poly(ester-carbonate-siloxane)s comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units.
  • the thermoplastic polymer comprise poly(ester-carbonate-siloxane)s comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units.
  • Embodiment 4 The method of Embodiment 1, wherein the thermoplastic polymer is a polyetherimide polymer or copolymer or a combination comprising at least one of the foregoing thermoplastic polymers.
  • Embodiment 5 The method of Embodiment 1, wherein the thermoplastic polymer is a polyphenylethersulfone polymer or copolymer or a combination comprising at least one of the foregoing thermoplastic polymers.
  • Embodiment 7 The method of any of the preceding Embodiments, wherein the non-brominated and non-chlorinated organic phosphorus-containing additive is selected from the group consisting of triphenyl phosphate, tri cresyl phosphates, tri xylyl phosphates, tri mesityl phosphates, bisphenol A diphosphates, resorcinol diphosphates, biphenol diphosphates, hydroquinone diphosphates, acetophenone bisphenol diphosphates, dihydroxy diphenyl ether diphosphates their oligomeric and polymeric counterparts, or a combination comprising at least one of the foregoing non-brominated and non-chlorinated organic phosphorus-containing additives.
  • the non-brominated and non-chlorinated organic phosphorus-containing additive is selected from the group consisting of triphenyl phosphate, tri cresyl phosphates, tri xylyl phosphates, tri mes
  • Embodiment 8 The method of any of the preceding Embodiments, wherein the non-brominated and non-chlorinated organic phosphorus-containing additive is selected from the group consisting of resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, their oligomeric and polymeric counterparts, or a combination comprising at least one of the foregoing non-brominated and non- chlorinated organic phosphorus-containing additives.
  • RDP resorcinol tetraphenyl diphosphate
  • the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A
  • their oligomeric and polymeric counterparts or a combination comprising at least one of the foregoing non-brominated and non- chlorinated organic phosphorus-containing additives.
  • Embodiment 9 The method of any of the preceding Embodiments, wherein the non-brominated and non-chlorinated organic phosphorus-containing additive has a weight average molecular weight 300 to 2000 Daltons and a boiling point of at least 300 degrees C.
  • Embodiment 10 The method of any of the preceding Embodiments, wherein the amount of the non-brominated and non-chlorinated organic phosphorus-containing additive is from 0.5% to 15 %, from 1% to 12%, or from 2% to 10% or any range within 1% to 30%, by weight, based on the weight of the thermoplastic polymer.
  • Embodiment 11 The method of any of the preceding Embodiments, wherein the forming a plurality of layers comprises melt-extruding layers a thermoplastic material.
  • Embodiment 12 The method of any of the preceding Embodiments, wherein the thermoplastic polymer composition has a glass transition temperature (Tg) as measured as per ASTM method D3418 from 100 to 250°C.
  • Tg glass transition temperature
  • Embodiment 13 The method of any of the preceding Embodiments, wherein the plurality of layers comprises at least twenty layers.
  • Embodiment 14 The method of any of the preceding Embodiments, wherein the thermoplastic polymer composition has less than 500 ppm of bromine or chlorine and has a change in melt viscosity as measured by ASTM method D4440-15 at 300°C for 30 minutes of less than 30% of the initial viscosity value.
  • Embodiment 15 An article made by any of the preceding method Embodiments.
  • Embodiment 16 An article useful in aircraft or other passenger conveyances comprising a plurality of layers of a material in a preset pattern of at least twenty fused, melt- extruded layers comprising a thermoplastic polymer composition, wherein the thermoplastic polymer composition comprises a polycarbonate polymer or copolymer, a polyetherimide polymer or copolymer, a polyarylethersulfone polymer or copolymer, or a combination comprising at least one of the foregoing thermoplastic polymers and a non-brominated and non- chlorinated organic phosphorus-containing that will lower the Tg of the thermoplastic polymer and wherein the article has a 2 minute integrated heat release rate of less than or equal to 65 kilowatt-minutes per square meter (kW-min/ni2) and a peak heat release rate of less than 65 kilowatts per square meter (kW/m2) as measured using the method of FAR F25.4, in accordance with Federal Aviation Regulation FAR 25
  • Embodiment 17 The article made by any of Embodiments 15-16, wherein the article has having a thickness of from 1 to 10 mm.
  • Embodiment 18 The article made by any of Embodiments 15-17, wherein the article contains at least 0.5 volume % of non-spherical voids.
  • Embodiment 19 The article made by any of Embodiments 15-18, wherein the article is made by monofilament deposition using monofilament strands having a diameter from 0.1 to 5.0 mm.
  • Embodiment 20 The article made by any of Embodiments 15-19, wherein the layers alternate in an overlapping pattern wherein at least half of the layers intersect at an angle of from 60 to 120 degrees.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function and/or objectives of the
  • compositions, methods, and articles are compositions, methods, and articles.

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Abstract

L'invention concerne des procédés de fabrication d'articles utiles dans un aéronef ou autres transports de passagers (et articles spécifiques fabriqués), ces procédés comprenant l'extrusion à chaud d'une pluralité de couches comprenant une composition polymère thermoplastique dans un motif prédéfini; et la fusion de la pluralité de couches pour former l'article; la composition polymère thermoplastique étant une combinaison de polymère ou de copolymère de polycarbonate, d'un polymère ou d'un copolymère de polyétherimide, d'un polymère ou d'un copolymère de polyaryléthersulfone, et d'un additif contenant du phosphore organique non bromé et non chloré, qui permet de réduire la Tg du polymère thermoplastique de 5 à 100 °C, l'article satisfaisant aux exigences de la Federal Aviation Regulation FAR 25.853 (d).
PCT/US2016/065516 2015-12-11 2016-12-08 Fabrication additive d'articles utiles pour aéronef Ceased WO2017100397A1 (fr)

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US20200384681A1 (en) * 2017-04-24 2020-12-10 Solvay Specialty Polymers Usa, Llc Method of making a three-dimensional object using ppsu
WO2022002628A1 (fr) * 2020-07-01 2022-01-06 Evonik Operations Gmbh Mousses de particules de pei à teneur en agent de soufflage résiduel définie
EP4406726A4 (fr) * 2021-09-21 2025-10-01 Adeka Corp Composition de résine thermoplastique, procédé de production d'un objet façonné, et objet façonné

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US4690997A (en) 1984-01-26 1987-09-01 General Electric Company Flame retardant wire coating compositions
US4808686A (en) 1987-06-18 1989-02-28 General Electric Company Silicone-polyimides, and method for making
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200384681A1 (en) * 2017-04-24 2020-12-10 Solvay Specialty Polymers Usa, Llc Method of making a three-dimensional object using ppsu
WO2022002628A1 (fr) * 2020-07-01 2022-01-06 Evonik Operations Gmbh Mousses de particules de pei à teneur en agent de soufflage résiduel définie
EP4406726A4 (fr) * 2021-09-21 2025-10-01 Adeka Corp Composition de résine thermoplastique, procédé de production d'un objet façonné, et objet façonné

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