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WO2024044062A1 - Particules thermoplastiques et leur procédé de fabrication - Google Patents

Particules thermoplastiques et leur procédé de fabrication Download PDF

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Publication number
WO2024044062A1
WO2024044062A1 PCT/US2023/030208 US2023030208W WO2024044062A1 WO 2024044062 A1 WO2024044062 A1 WO 2024044062A1 US 2023030208 W US2023030208 W US 2023030208W WO 2024044062 A1 WO2024044062 A1 WO 2024044062A1
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Prior art keywords
acid
condensation
condensation polymer
polymer powder
oil
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Thomas Fry
John G. Eue
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Jabil Inc
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Jabil Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

Definitions

  • This disclosure relates to additive manufacturing thermoplastic particulates useful for additive manufacturing.
  • the disclosure is directed to formation of condensation polymer (e.g., polyamide) particulates useful for additive manufacturing.
  • condensation polymer e.g., polyamide
  • additive manufacturing also known as three-dimensional (3D) printing
  • 3D printing constitutes a significant advance in the development of not only printing technologies, but also of experimental, prototyping, and product development capabilities.
  • 3D printing allows for the formation of physical objects of virtually any geometry.
  • an object to be built is created virtually as a 3D digitally-modeled image using computer-aided design (CAD) software.
  • CAD computer-aided design
  • the object model is virtually “sliced” into thin layers, which ultimately provide parameters of how the model will be physically built by the 3D printer.
  • This virtual slicing is needed because conventional methods of 3D-printing involve a print head that successively deposits material in thin layers according to the geometry of the modeled image based on the printing parameters for each layer.
  • common filament-based methods e.g., fused filament fabrication “FFF”, see for example, U.S. Pat. Nos.
  • a print head deposits heated material (e.g, thermoplastic polymer) while moving in multiple linear directions parallel to the printer base, while the base or print head moves stepwise in the vertical dimension away from each other. The print head continues depositing the material until the final, uppermost layer of the object has been deposited and the object is thus fully formed.
  • heated material e.g, thermoplastic polymer
  • Powder-based methods of additive manufacturing include the following: Selective laser sintering (SLS) is a 3D-printing technique that uses a laser to fuse powder material in successive layers (see, for example, U.S. Pat. No. 5,597,589).
  • High-speed sintering (HSS) and multi-jet fusion (MJF) 3D-printing employ multiple jets that similarly deposit successive layers of infrared-absorbing (IR-absorbing) ink onto powder material, followed by exposure to IR (infra-red) energy for selective melting of the powder layer.
  • Electrophotographic 3D-printing employs a rotating photoconductor that builds the object layer-by-layer from the base.
  • SLS selective laser sintering
  • MJF multi-jet fusion
  • HSS high-speed sintering
  • 3D-printing methods use the same type of free-floating, non-fixed powder bed. They generally have the same material requirements for compatibility with the printing process since the additively built object will experience similar stresses, only with different heating mechanisms to obtain the melt phase.
  • a free-body diagram of a 3D printed object can be used to determine the residual stresses expected in the printed object. This is necessary for successfully building the object. If the residual stress is too high, the object will deform or be deformed beyond acceptable tolerances.
  • condensation polymers such as polyamide or polyester have typically been made by bulk polymerization processes, which allows for ease of removal of condensation by-products (e.g., water), to realize the desired molecular weight, weight distribution, crystallinity and melt flow rate.
  • condensation by-products e.g., water
  • the polymers typically are cryogenically ground.
  • these processes require substantial energy usage and losses due to rework (e.g., unusable fines powders from the grinding process).
  • the grinding processes leads to fracturing resulting in powders with angularity and asperities that inhibit powder flow, which in many instances require the addition of flow aids.
  • Polyesters made by emulsion polymerization in water have been described in U.S.
  • Polyamides have been produced by interfacial polymerization where a diamine is dissolved in water and reacted with diacid halide dissolved in an immiscible solvent and to maintain reactivity, the polymer is continuously withdrawn such as described in U.S. Pat. Nos. 2,708,617 and 3,068,527. Likewise, emulsion polymerization of polyamide in a similar fashion has been described such as described in DE1903266.
  • each of these methods suffers from one or more of: the inability to tailor the molecular weight of the formed polymer, the need to use a diacid chloride requiring the neutralization and removal of HC1, and inability to tailor the size and shape of the polymer formed.
  • Applicants have discovered a method to form useful condensation polymers having the desired shape and size useful for additive manufacturing.
  • the method allows for creating such powders in the absence of a diacid halide directly without having to grind the polymer.
  • the method allows for the formation of condensation polymers having the desired size and shape for additive manufacturing in the absence of any chlorine contamination, while still realizing useful molecular weights and melt flows for powder bed fusion additive manufacturing methods.
  • a first aspect of the invention is a method of forming a condensation polymer powder comprising, adding a first reactant comprised of a first condensation monomer to an oil to form an emulsion, adding a second reactant comprised of a second condensation monomer to the emulsion, and reacting the first and second reactant to form the condensation polymer powder, wherein agitation is supplied during at least a portion of the method and the oil has a boiling point above the condensation polymer’s melting temperature, and separating the condensation polymer powder from the oil.
  • condensation polymerization may be performed at elevated temperatures where an emulsion of the forming polymers under agitation, which may include ultrasonic agitation, may form polymeric particles having desirable size, morphology and other characteristics such as melt flow in the absence of chlorine.
  • Boiling temperature or boiling point herein is the “normal boiling temperature”, which is taken as the boiling temperature at 1 bar of pressure, with it being understood that the boiling point of the oil at elevated pressures may be at a high temperature suitable for the process herein.
  • the oil may have a boiling point range due to the presence of differing molecular weight constituents, and as such the boiling point may be taken as the initial boiling point as per ASTM D86. It is also recognized that some small fraction of lower boiling point constituent of the oil may be removed during the process while still being able to realize the desired condensation polymer powder.
  • Another aspect is a method of forming a condensation polymer powder, comprising forming a precursor salt from a first condensation monomer and second condensation monomer, heating under agitation the precursor salt in an oil to form an emulsion, allowing the precursor salt to polymerize to form molten polymer particles having a melt temperature, cooling the molten polymer particles below the melt temperature of the polymer molten polymer particles to form the condensation polymer and separating the condensation polymer from the oil.
  • the first and second condensation monomers may be reacted at a lower temperature to form a stable salt at ambient conditions (e.g., ⁇ 25 °C) to about 100 °C, which is subsequently mixed with the oil and heated to a temperature where the salt polymerizes and forms a molten polymeric emulsion in the oil that may be allowed to polymerize via bulk polymerization in the formed emulsion droplets.
  • a suitable solvent e.g., polar protic or polar aprotic solvent
  • a monomer such as a salt (e.g., organic dicarboxylic acid halide) in water when performing the process.
  • the polar aprotic solvent may be an aliphatic or cyclic ether, ketone or combination thereof. Removal of any by-products may be carried out by any known techniques including, for example, the application of vacuum, venting to atmosphere or flowing gases to remove by products such as water. Likewise, the reactants may be reacted to form an oligomer that may be heated and emulsified to form the desired condensation polymer powder having the desired characteristics.
  • polyesters may be made using any suitable organic polyfunctional acid (e.g., diacid) or corresponding anhydride and a polyfunctional alcohol (e.g., dialcohol) such as described in U.S. Pat. No. 4,355,154, incorporated herein by reference.
  • the condensation polymer may be a polyamide and the monomers being any suitable such as those known in the art (e.g., polyfunctional amines and polyfunctional diacids or corresponding anhydrides or halides) such as described in U.S. Pat. Nos.
  • Exemplary acid halides may include an aliphatic dicarboxylic acid halide of oxalic acid, malonic acid, succinic acid, adipic acid glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or combination thereof.
  • Exemplary acid halides may include aromatic dicarboxylic acid of phenylenediacetic acid, p-phenylenediacetic acid, m-benzenedipropionic acid, p-benzenedipropionic acid, and other higher members of the class of metaor parabenzenealkyl dicarboxylic acids.
  • Exemplary first condensation monomers when making a polyamide may include one or more of carboxylic acid comprising one or more of phenylenediacetic acid, p- phenylenediacetic acid, m-benzenedipropionic acid, p-benzenedipropionic acid, and other higher members of the class of meta or para-benzenealkyl dicarboxylic acids and the second condensation monomer may be comprised of one or more of hexamethylenediamine, tetramethylenediamine, octamethylenediamine, decamethylenediamine and dodecamethylenediamine, m-xylylenediamine, bis(4-aminophenyl)methane, bis(4- aminophenyl)propane-2,2 and bis(4-aminocyclohexyl)methane.
  • the first monomer and second monomer are added to the oil to form an emulsion, which requires agitating at least during some portion of the method.
  • the agitation may be any suitable, but typically requires high shear which may be provided by known apparatus such as extruders (e.g., twin screw), banbury mixers, colloid mills, homogenizers, ultrasonic agitation and a combination thereof. It may be desirable to provide high shear by physical mixing (e.g., the aforementioned other than ultrasonic agitation) further supplemented with ultrasonic agitation.
  • the agitation may be provided the entire time of the process but may not be necessary after emulsification and polymerization of the particles, wherein it may be desirable to reduce the shear upon cooling below the melt temperature of the particulate polymers that have been formed.
  • the shear rate may be increased or supplemental shear induced by ultrasonic energy to form the emulsion and during polymerization with the energy input varied to realize the desired size and size distribution.
  • simple mixing without any ultrasonic energy may be applied.
  • the oil may be any oil that may be heated to a temperature above where the desired condensation polymer becomes molten and flows like a liquid, allowing for example, the formation of spherical particulates within the oil that then may be cooled and separated.
  • the oil may not necessarily have such a high temperature, for example, when using an acid halide as one of the monomers when forming a polyamide.
  • the reaction may take place at lower temperatures within the emulsion in a similar manner where the particulates at a lower temperature may be immiscible in the oil and the particles and solvent removed after forming the desired condensation polymer.
  • oils may include hydrocarbon/mineral-based oils, vegetable oils and silicone oils such as those known in the art.
  • the oil desirably has a boiling temperature above the onset melt temperature of the condensation polymer being formed or in the case of an amorphous polymer, where the polymer becomes molten and flows like a liquid.
  • the oil has a boiling temperature that is at least 10 °C, 20 °C, or 50 °C above the melt temperature of the condensation polymer.
  • the boiling point is at least about 150 °C, 175 °C, 200 °C, 225 °C or 250 °C to any practical temperature such as 500°C or 400 °C being usually suitable.
  • Elevated pressures may be utilized if desired.
  • the viscosity of the oil may be any useful viscosity so long as an emulsion may be prepared having the desired particle/droplet size of the condensation polymer, but it may be useful to have an oil that is more viscous such as one that has a viscosity at room temperature ( ⁇ 25 °C) that is at least about 1, 10, 100 or 1000 centipoise.
  • Melt temperature herein shall be the onset melt temperature unless explicitly state otherwise and may be determined as described in ASTM D3418-5. Unless otherwise specified the heating rate of any DSC plot is 20 °C/minute.
  • the boiling temperature of the oil may be determined by ASTM D86.
  • Illustrative oils may include silicon oils such as those described in U.S. Pat.
  • the hydrocarbon/mineral oils may include any known such as those commercially available (API Groups I- III).
  • the oils may include glycol ethers such as those commonly used in brake fluids and described in US2009/0099048, incorporated herein by reference.
  • the oils may include synthetic oils (e.g., API group TV and V) such as low molecular weight olefins such as described in US Pat. No. 7,687,442, incorporated herein by reference.
  • the mineral oil may be a white mineral oil such as “mineral oil, light, white” from VWR Life Science, having CAS-No 8042-47-5, EC No.
  • the white mineral oil may have a boiling point range from 260 to 427°C.
  • the oil may be vegetable oil or animal fat which may be purified, refined or hydrolyzed such as those having useful smoke points or boiling points (e.g., above 200 °C). Examples include avocado, clarified butter, canola, com, cotton seed, grape seed, mustard, olive, palm, pecan, peanut safflower sesame, sunflower and blends thereof.
  • the reacting may be at any temperature allowing for the formation of the condensation polymer and may vary depending on the particular condensation polymer desired.
  • the condensation reaction may take place at multiple temperatures or upon slowly heating (e.g., less than 20 °C, 10 °C, 5 °C or 2 °C per minute) the emulsion to facilitate the formation of the condensation polymer without losses of monomer or precursor of the monomer.
  • a high temperature may not be required (room temperature to 50 °C may be sufficient).
  • the temperature is at least about 150 °C, 175 °C, 200 °C, 225 °C or 250 °C to 350 °C or 300 °C.
  • the condensation polymer may be formed at an elevated temperature to cool below the melt temperature of the polymer particles and above the glass transition temperature of the polymer particles, which may be useful for inducing crystallization of the polymer particles.
  • the time at this crystallization temperature may be any useful for inducing the desired crystallization. Typically, the time at the crystallization temperature is from 2 to 5 minutes to 5, 3 or 1 hour.
  • the cooling rate may be sufficiently slow from the melt temperature to the glass transition temperature of the polymer particles to induce crystallization (e.g., 1 °C/min to 0.01 °C), which may be varied as well (e.g., slower cooling near the melt temperature of the polymer and faster near the glass transition temperature).
  • the temperature of the reacting may any suitable to form the desired condensation polymer powder particles such as 3 minutes, 5 minutes, 10 minutes to 10 hours, 5 hours, 2 hours or 1 hour.
  • the polyamide may be any of those known in the art and and commonly are semi- crystalline as described from col. 4, line 7 to col. 5, line 22 of U.S. Pat. No. 5,391 ,640, incorporated herein by reference.
  • the polyamide may be amorphous as described from col. 5, line 23 to col. 8, line 12 of U.S. Pat. No. 5,391,640, incorporated herein by reference.
  • polystyrene resin examples include polypyrrolidone (nylon 4), polycaprolactam (nylon 6), polyheptanolactam (nylon 7), polycaprylactam (nylon 8), polynonanolactam (nylon 9), polyundecaneolactam (nylon 11), poly dodec anolactam (nylon 12), poly(tet-ramethylenediamine-co-oxalic acid) (nylon 4,2), poly(tetramethylenediamine-co-adipic acid) (nylon 4,6), poly(tetramethylenediamine-co-isophthalic acid) (nylon 4,1), polyhexamethylene azelaiamide (nylon 6,9), polyhexamethylene sebacamide (nylon 6,10), polyhexa- 5 methylene isophthalamide (nylon 6, IP), polymetaxylylene adipamide (nylon MXD6), the polyamide of ndodecanedioic acid and hex
  • the polyimide may be any of those known in the art and desirably are known aromatic polyimides.
  • Aromatic polyimides that may be suitable are described in U.S. Pat. Nos. 3,179,631; 3,249,588 and 4,755,555, each incorporated herein by reference.
  • Examples of useful polysulfones may include polyarylethersulfones (PAES) which may be represented by:
  • n is any integer value that gives rise to the PAES having an weight average molecular weight (Mw) anywhere from 1, 10, or 20 to 1000, 500 or 200 kDa
  • Mw weight average molecular weight
  • m typically varies from 0 to 10
  • each occurrence of R1 represents an aromatic ring or fused rings of about 5-10 carbon atoms, such as but not limited to: 1,2-, 1,3-, or 1 ,4-phcnylcnc, or a diphcnylcnc such as but not limited to 4,4’ -diphenylene
  • each occurrence of R2 is independently C1-C20 alkyl, C5-C18 or C5-C12 aromatic ring or fused rings consisting of 5-10 carbon atoms, or a combination thereof.
  • R 1 and R 2 may be the residue of an aryl or diaryl compound:
  • m has an integer value greater than or equal to zero (typically from 1 to 10, 6, 5, 4, 3, or 2), and each R2 is a residue of a dihydroxy compound such as an aromatic dihydroxy compound:
  • each R3, R4, and R5 is independently, for example, but not limited to: a halogen atom (e.g., chlorine or bromine), a C3-20 alkoxy, a Cl-20 hydrocarbyl group (e.g., a Cl-20 alkyl, a halogen-substituted Cl-10 alkyl, a C6-10 aryl, or a halogensubstituted C6-10 aryl); and p, q, and r are each independently integers of 0 to 4, such that when p, q, or r is less than 4, the valence of each unsubstituted carbon of the ring is filled by hydrogen; and X represents a bridging group connecting the two phenolic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (preferably para) to each other on the C6 arylene group, and the X group
  • a halogen atom e.g.,
  • Specific dihydroxy compounds include but are not limited to: resorcinol; 2,2-bis(4- hydroxyphenyl)propane (“bisphenol A” or “BPA”, in which in which each of aryl rings is parasubstituted and X is isopropylidene in formula (3)); 3,3-bis(4-hydroxyphenyl)phthalimidine; 2- phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (also known as ‘W-phenyl phenolphthalein bisphenol”, “PPPBP”, or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one); 1, 1 -bis(4- hydroxy-3-methylphenyl)cyclohexane; l,l-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethyl- cyclohexane (also known as “isophorone bisphenol”).
  • polyarylethersulfones that are suitable may any one or more of:
  • the method may produce a condensation polymer powder that may be additively manufactured in the absence of a flow aid.
  • the powder has a sphericity which aids in flowability, and as derived from micrograph images of individual particles, may be expressed in terms of circular character, or circularity, where individual particle circularity is defined as the 4TTA/P2, where A is the area of the particle and P is the perimeter length of the particle, both as viewed from a random perspective.
  • Sphericity a related parameter, is derived as the square root of circularity. Circularity is a numerical value greater than zero and less than or equal to one. A perfectly circular particle is referred to as having a circularity of 1.00.
  • Tables of population circularity data are represented in such a way that various levels of circularity (e.g., 0.65, 0.75, 0.85, 0.90, and 0.95) arc accompanied by percentages of the particle sample population with a circularity greater than the tabulated value.
  • the circularity is determined at a solidity filter level of 0.9 or 0.95.
  • Solidity filter is a filter used to remove overlapping particles in a 2-dimensional micrograph available in commercial image analysis software. Solidity in essence is the area of a particle over the area (particle area) of an area defined by the major and minor axis of the particle area in a 2-dimensional micrograph. Particle size and shape can be measured by any suitable methods known in the art to measure particle size by diameter.
  • the particle size and shape are determined by laser diffraction as is known in the art.
  • particle size can be determined using a laser diffractometer such as the Microtrac S3500 with static image analysis accessory using PartAnSI software to analyze the captured images of the particles.
  • a laser diffractometer such as the Microtrac S3500 with static image analysis accessory using PartAnSI software to analyze the captured images of the particles.
  • at least about 65%, 70%, 80%, 95% or 99% of the particles (by number) have a circularity is at least about 0.8, 0.85, 0.9 or 0.95 for the powders separated and classified from the reactor without further treatment other than purification.
  • the separating may be an suitable separation process such as those known in the art. Examples include filtration, flotation, and centrifugal separation. After separation the polymer particles may be washed with a solvent to further remove any residual oil from the particles. Examples of solvents useful for washing the particles (washing solvents) may include one or more of a ketone (e.g., acetone), toluene, alkane, and an alcohol.
  • the condensation polymer powders without the addition of any flow aid generally have a flowability of at least about 0.5 g/s, 1 g/s or 2 g/s to any practically achievable rate (e.g., 50 g/s) using a 15-mm nozzle as determined by Method A of ASTM D 1895.
  • the method allows for the formation of condensation polymers having some crystallinity even though upon heating at a slow temperature to its melting temperature will become amorphous.
  • the crystallinity is typically at least about 15% by weight to essentially crystalline, with higher degrees of crystallinity being desirable.
  • the crystallinity is anywhere from 20%, 25% or 30% to essentially crystalline, 90%, 80%, 75%, 60% or 55%.
  • the crystallinity may be determined by any suitable methods such as those known in the art.
  • the percent crystallinity may be determined by x-ray diffraction including, for example, wide angle x-ray diffraction (WAXD), such as by using a Rigaku Smart Lab x-ray diffractometer, or by differential scanning calorimetry (DSC), such as by using a TA Instruments DSC250 differential scanning calorimeter ASTM D3418- 5.
  • WAXD wide angle x-ray diffraction
  • DSC differential scanning calorimetry
  • the condensation polymer may have any DSC melt peak enthalpy useful for making a powder useful in additive manufacturing such as SLS.
  • the enthalpy is at least 3 joules/gram, but desirably is at least 5, 10, 20, 30, 40, 50, 60, 70 or 75 joules/gram or more to any practical amount such as 200 joules/gram.
  • the enthalpy of the DSC melt peak may be determined according to the manner described by ASTM D3418-5.
  • the condensation polymer powder generally has a particle size and size distribution that is useful for making additive manufactured articles and typically have, and an average or median particle size (D50), by volume, from about 1 micrometer (pm), 10 pm, 20 pm, 30 pm or 40 pm to 150 pm, 125 pm, 110 pm or 100 pm. Likewise, to enable consistent heating and fusion of the powder, it desirably has a D90 of at most 300 pm, 200 pm or 150 pm. To aid in flowability the powder desirably has a D10 of at least 0.1 pm, 0.5 pm or 1 pm by volume.
  • D50 average or median particle size
  • D90 means the particle size (equivalent spherical diameter) in the particle size distribution, where 90% by volume of the particles are less than or equal to that size; similarly, D50 means the particle size (equivalent spherical diameter) in the particle size distribution, where at least 50% by volume of the particles are less than that size, and D10 means the particle size (equivalent spherical diameter) in the particle size distribution, where at least 10% by volume of the particles are less than that size.
  • the particle size may be determined by any suitable method such as those known in the art including, for example, laser diffraction or image analysis of micrographs of a sufficient number of particles (-100 to -200 particles).
  • a representative laser diffractometer is one produced by Micro trac such as the Micro trac S3500.
  • the condensation polymer powder may be further comprised of useful additives such as those known in the art for making articles such as additive manufactured articles.
  • the powder may have one or more of a UV stabilizer, filler, lubricant, plasticizer, pigment, flow aid, flame retardant, or solvent.
  • the powder is essentially free of solvent and halide (i.e., at most a trace amount, which may be at most 10 parts per million (ppm) by weight of the composition, 1 ppm).
  • the amount of any particular additive may be any useful amount to realize a particular property for printing or characteristic of the article formed therefrom.
  • the amount of the additive or additives, when present, is at most about 50%, 25%, 10% or 5% by volume of the composition.
  • the flow aid may be any known compound for improving the flowability of powders with fumed silica being an example (e.g., Aerosil 200).
  • the condensation polymer powders of this invention allow for the formation of shaped articles that do not deform or possess undesirable amounts of residual stress.
  • the compositions of this invention may be made into a body by an additive manufacturing method such as SLS, MJF, HSS or electrophotography.
  • SLS a layer of the condensation polymer powder may be deposited on a bed at a fixed temperature below the melting temperature of the powder and a predetermined (selected) area of the bed is sintered (fused) together using a heating source such as a laser controlled and directed as described above. Layers are then in succession deposited and sintered to the preceding layer and within the layer to build up an additive manufactured part.
  • the “operating window” for additive manufacturing semicrystalline thermoplastic polymers is the temperature difference between the onset temperature at which the material melts to the onset temperature at which it recrystallizes (“Tc”), which generally is as large as possible.
  • the method may allow for the tuning of the melt peak shape and onset temperature.
  • the condensation polymer powder may be further optimized wherein the operating window may be anywhere from 5 °C, 10 °C, or 20 °C to any realized temperature differences such as 60 °C, 50 °C, 30 °C, or 25 °C.
  • PA 6,10 Powder Synthesis 4.3mL of sebacoyl dichloride was added to 40mL of cyclohexanone and stirred in a beaker to homogenize. In a separate beaker 6.7mL of 6M NaOH and 20mL IM hexamethylenediamine were stirred and homogenized. 200mL of white mineral oil was added to a Erlenmeyer flask and stirred vigorously. The sebacoyl solution was added to mineral oil flask and allowed to stir for several minutes. Small “bubbles” can be observed of this solution inside the mineral oil medium. After several minutes, the HMDA solution was added dropwise to the mineral oil solution. Almost immediately a white precipitate is observed.
  • adipic acid is dissolved in 200 mL of deionized water and stirred until completely in solution. The water is heated to approximately 40 °C to fully dissolve the acid.
  • 1,6-diaminohexane is dissolved in 200 mL of deionized water. The two solutions are then combined, and excess water is boiled off to produce 75mL of PA 6,6 salt solution.
  • the PA 6,6 salt solution is added to 100 mL of 5000 cSt silicone oil in a reactor flask and heated at a rate of about 3 °C/min to 200 °C while stirring at 350 rpm forming an emulsion of the salt solution in the oil.
  • the emulsion is held at 200 °C for approximately 20 hours while stirring. The temperature is then increased to 270 °C and held for about 4 hours. Heat is then shut off and when the temperature of the emulsion drops below 100 °C, 100 mL of xylene was added to the emulsion. After stirring for several minutes, the slurry was then vacuum filtered through a Buchner funnel. After the oil/xylene mixture was completely filtered about 200 mL of xylene was poured into the Buchner funnel to wash any residual oil off the powder. The powder is then placed in an oven at 80 °C to dry.

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Abstract

Des poudres de polymères de condensation pour fabrication additive peuvent être obtenues par émulsification de monomères de condensation, des intermédiaires des monomères tels que des oligomères ou des sels dans une huile à haute température, l'émulsion étant chauffée à une température de polymérisation à une température supérieure à la température de fusion du polymère pour polymériser et réaliser des particules ayant la forme des gouttelettes émulsifiées lors du refroidissement après polymérisation.
PCT/US2023/030208 2022-08-22 2023-08-15 Particules thermoplastiques et leur procédé de fabrication Ceased WO2024044062A1 (fr)

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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708617A (en) 1951-05-12 1955-05-17 Du Pont Formation of films and filament directly from polymer intermediates
US3068527A (en) 1958-12-09 1962-12-18 Du Pont Process for the production of a fibrid slurry
US3179631A (en) 1962-01-26 1965-04-20 Du Pont Aromatic polyimide particles from polycyclic diamines
US3249588A (en) 1962-06-06 1966-05-03 Du Pont Process for preparing finely divided polyimide particles of high surface area
DE1903266A1 (de) 1969-01-23 1970-07-30 Wolff Walsrode Ag Grenzflaechenkondensierte Polyamide und Verfahren zu ihrer Herstellung
US4355154A (en) 1981-10-06 1982-10-19 Dow Corning Corporation Method for preparing condensation polymers by emulsion polymerization
US4755555A (en) 1985-04-26 1988-07-05 E. I. Du Pont De Nemours And Company Polyimide molding resins and molded articles
US4863646A (en) 1986-10-23 1989-09-05 Shinto Paint Co., Ltd. Method of producing fine particles of thermoplastic resin
US5121329A (en) 1989-10-30 1992-06-09 Stratasys, Inc. Apparatus and method for creating three-dimensional objects
US5391640A (en) 1992-04-14 1995-02-21 Alliedsignal Inc. Miscible thermoplastic polymeric blend compositions containing polyamide/amorphous polyamide blends
US5503785A (en) 1994-06-02 1996-04-02 Stratasys, Inc. Process of support removal for fused deposition modeling
US5597589A (en) 1986-10-17 1997-01-28 Board Of Regents, The University Of Texas System Apparatus for producing parts by selective sintering
US20090099048A1 (en) 2007-10-15 2009-04-16 Dow Global Technologies Inc. Functional fluid composition for improving lubricity of a braking system
US7687442B2 (en) 2004-03-17 2010-03-30 Dow Global Technologies Inc. Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils
CN108395530A (zh) * 2017-02-06 2018-08-14 中国石油化工股份有限公司 一种基于反相悬浮聚合法制备用于选择性激光烧结尼龙粉末的方法
CN110144040A (zh) * 2019-05-14 2019-08-20 东华大学 一种降黏添加剂改性尼龙66复合材料及其制备和应用

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708617A (en) 1951-05-12 1955-05-17 Du Pont Formation of films and filament directly from polymer intermediates
US3068527A (en) 1958-12-09 1962-12-18 Du Pont Process for the production of a fibrid slurry
US3179631A (en) 1962-01-26 1965-04-20 Du Pont Aromatic polyimide particles from polycyclic diamines
US3249588A (en) 1962-06-06 1966-05-03 Du Pont Process for preparing finely divided polyimide particles of high surface area
DE1903266A1 (de) 1969-01-23 1970-07-30 Wolff Walsrode Ag Grenzflaechenkondensierte Polyamide und Verfahren zu ihrer Herstellung
US4355154A (en) 1981-10-06 1982-10-19 Dow Corning Corporation Method for preparing condensation polymers by emulsion polymerization
US4755555A (en) 1985-04-26 1988-07-05 E. I. Du Pont De Nemours And Company Polyimide molding resins and molded articles
US5597589A (en) 1986-10-17 1997-01-28 Board Of Regents, The University Of Texas System Apparatus for producing parts by selective sintering
US4863646A (en) 1986-10-23 1989-09-05 Shinto Paint Co., Ltd. Method of producing fine particles of thermoplastic resin
US5121329A (en) 1989-10-30 1992-06-09 Stratasys, Inc. Apparatus and method for creating three-dimensional objects
US5391640A (en) 1992-04-14 1995-02-21 Alliedsignal Inc. Miscible thermoplastic polymeric blend compositions containing polyamide/amorphous polyamide blends
US5503785A (en) 1994-06-02 1996-04-02 Stratasys, Inc. Process of support removal for fused deposition modeling
US7687442B2 (en) 2004-03-17 2010-03-30 Dow Global Technologies Inc. Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils
US20090099048A1 (en) 2007-10-15 2009-04-16 Dow Global Technologies Inc. Functional fluid composition for improving lubricity of a braking system
CN108395530A (zh) * 2017-02-06 2018-08-14 中国石油化工股份有限公司 一种基于反相悬浮聚合法制备用于选择性激光烧结尼龙粉末的方法
CN110144040A (zh) * 2019-05-14 2019-08-20 东华大学 一种降黏添加剂改性尼龙66复合材料及其制备和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAS, no. 8042-47-5

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