Light-absorbing thermoplastic polymer particles and methods of making and using the same

Abstract

A thermoplastic polymer particle containing a light absorber (OACTP particle) can be prepared by a method comprising: mixing a mixture comprising a thermoplastic polymer, a carrier fluid immiscible with the thermoplastic polymer, and optionally an emulsion stabilizer at a temperature greater than the melting point or softening temperature of the thermoplastic polymer and at a sufficiently high shear rate to disperse the thermoplastic polymer in the carrier fluid; cooling the mixture to below the melting point or softening temperature of the thermoplastic polymer to form solidified particles comprising the thermoplastic polymer; separating the solidified particles from the carrier fluid; and exposing the solidified particles to a light absorber to produce the OACTP particle.

Description

Technical Field

[0001] This disclosure relates to thermoplastic polymer particles comprising light-absorbing molecules. This disclosure also relates to methods for preparing and using such particles. Background Technology

[0002] Counterfeiting and imitation are among the most pressing issues in consumer markets and the modern global economy. The International Chamber of Commerce estimates that counterfeiting will account for approximately $4.2 trillion of the global economy in 2022.

[0003] Anti-counterfeiting measures may include holograms and imprints to provide product authentication. However, these measures are typically used as a supplement to the packaging of goods, rather than being directly incorporated into the goods. Summary of the Invention

[0004] This invention relates to thermoplastic polymer particles containing light-absorbing molecules such as chromophores and / or fluorophores. This disclosure relates to methods for preparing and using such particles. The particles described herein (especially highly spherical thermoplastic polymer particles) can, among other things, be used as starting materials for additive manufacturing. Furthermore, light absorbers can be used to identify, track, authenticate, and / or determine the health status of articles made from thermoplastic polymer particles containing light absorbers.

[0005] The methods disclosed herein include: mixing a mixture comprising a thermoplastic polymer, a carrier fluid immiscible with the thermoplastic polymer, and optionally an emulsion stabilizer at a temperature above the melting or softening temperature of the thermoplastic polymer and at a sufficiently high shear rate to disperse the thermoplastic polymer in a carrier fluid; cooling the mixture to below the melting or softening temperature of the thermoplastic polymer to form solidified particles comprising the thermoplastic polymer; separating the solidified particles from the carrier fluid; and exposing the solidified particles to a light absorber to produce thermoplastic polymer particles containing the light absorber (OACTP particles).

[0006] The methods disclosed herein include: mixing a mixture comprising a thermoplastic polymer, a carrier fluid immiscible with the thermoplastic polymer, a light absorber, and optionally an emulsion stabilizer at a temperature greater than the melting or softening temperature of the thermoplastic polymer and at a shear rate sufficiently high to disperse the thermoplastic polymer in a carrier fluid; cooling the mixture to below the melting or softening temperature of the thermoplastic polymer to form solidified OACTP particles comprising the thermoplastic polymer and the light absorber; and separating the solidified OACTP particles from the carrier fluid.

[0007] The compositions disclosed herein also include: OACTP particles comprising a thermoplastic polymer and a light absorber non-covalently bonded to the thermoplastic polymer, wherein the particles have a sphericity of about 0.90 to about 1.0.

[0008] The method disclosed herein also includes: depositing the OACTP particles described herein, optionally combined with other thermoplastic polymer particles, onto a surface in a specified shape; and once deposited, heating at least a portion of the particles to promote their consolidation to form a solidified body.

[0009] The methods disclosed herein also include: extruding a filament comprising one or more of the OACTP-polyamides disclosed herein (and optionally one or more other thermoplastic polymers and / or one or more compatibilizers) and passing it through an orifice, wherein the filament becomes a polymer melt during extrusion; depositing the polymer melt as a first layer on a platform; cooling the layer; depositing an additional layer of polymer melt on the first layer; cooling the additional layer; and repeating the deposition and cooling of at least one additional layer to produce a 3D shape.

[0010] The methods disclosed herein also include: extruding a polymer melt containing one or more of the OACTP-polyamides disclosed herein (and optionally one or more other thermoplastic polymers and / or one or more compatibilizers) and passing it through an orifice to produce films, fibers (or filaments), granules, pellets, etc. Attached Figure Description

[0011] The accompanying drawings are included to illustrate certain aspects of the embodiments and should not be considered as exclusive embodiments. As will be appreciated by those skilled in the art who benefit from this disclosure, the disclosed subject matter is capable of considerable modifications, alterations, combinations, and equivalents in form and function.

[0012] Figure 1 This is a flowchart of a non-restrictive example method disclosed herein. Detailed Implementation

[0013] 3D printing (also known as additive manufacturing) is a rapidly developing technology field. Although 3D printing has traditionally been used for rapid prototyping activities, the technology is increasingly being used to produce commercial and industrial items that may have structural and mechanical tolerances that are completely different from those of rapid prototypes.

[0014] This invention relates to thermoplastic polymer particles containing light-absorbing molecules such as chromophores and / or fluorophores. More specifically, the light absorber is non-covalently bonded (e.g., via hydrogen bonds, ionic bonds, and / or π-π stacking of aromatic polymers and fluorophores) to the particles. Hereinafter, thermoplastic polymer particles containing light absorbers non-covalently bonded to the polymer particles are abbreviated as OACTP particles.

[0015] The particles described herein (especially highly spherical thermoplastic polymer particles) can, among other things, be used as starting materials for additive manufacturing. Furthermore, light absorbers can be used to identify, track, authenticate, and / or determine the health status of articles made from thermoplastic polymer particles containing light absorbers.

[0016] Definition and testing methods

[0017] As used herein, the term "immiscible" refers to a mixture of components that, when combined, form two or more phases having a solubility of less than 5% by weight in each other at ambient pressure and room temperature or the melting point of the components (if they are solid at room temperature). For example, polyethylene oxide having a molecular weight of 10,000 g / mol is solid at room temperature and has a melting point of 65°C. Therefore, if a material that is liquid at room temperature and said polyethylene oxide have a solubility of less than 5% by weight in each other at 65°C, then said polyethylene oxide is immiscible with said material.

[0018] As used herein, the term "light absorber" refers to a molecule or part thereof that absorbs ultraviolet or visible light.

[0019] As used in this article, the term "chromophore" refers to a light absorber in which light absorption imparts color.

[0020] As used in this article, the term "fluorophore" refers to a light absorber that re-emits absorbed photons at different wavelengths.

[0021] As used herein, the term "thermoplastic polymer" refers to a plastic polymer material that reversibly softens and hardens upon heating and cooling. Thermoplastic polymers encompass thermoplastic elastomers.

[0022] As used herein, the term "elastomer" refers to a copolymer comprising crystalline "hard" segments and amorphous "soft" segments. For example, in the case of polyurethane, the crystalline segments may comprise a portion of a polyurethane having urethane functional groups and optional chain extender groups, and the soft segments may comprise polyols.

[0023] As used herein, the term "polyurethane" refers to the polymer reaction product between diisocyanate, polyol and optional chain extender.

[0024] As used herein, the term "oxide" refers to both metal oxides and non-metal oxides. For the purposes of this disclosure, silicon is considered a metal.

[0025] As used herein, the terms “associative,” “associated,” and their grammatical variations refer to the chemical bonding and / or physical adhesion between the emulsion stabilizer and the surface. Without being theoretically limited, it is believed that the association between the polymer and the emulsion stabilizer described herein is primarily physical adhesion via hydrogen bonding and / or other mechanisms. However, chemical bonding can occur to some extent.

[0026] As used herein, the term “embedded” in relation to the surface of nanoparticles and polymer particles means that the nanoparticles extend at least partially into the surface such that the polymer contacts the nanoparticles to a greater extent than would be achieved if the nanoparticles were simply laid on the surface of the polymer particles.

[0027] In this document, D10, D50, D90, and diameter span are primarily used to describe particle size. As used herein, the term "D10" refers to a diameter in which 10% of the sample (unless otherwise specified, on a volume basis) consists of particles with a diameter smaller than said diameter value. As used herein, the term "D50" refers to a diameter in which 50% of the sample (unless otherwise specified, on a volume basis) consists of particles with a diameter smaller than said diameter value. As used herein, the term "D90" refers to a diameter in which 90% of the sample (unless otherwise specified, on a volume basis) consists of particles with a diameter smaller than said diameter value.

[0028] As used herein, the terms “diameter span” and “span” and “span size” provide an indication of the width of the grain size distribution when referring to diameter and are calculated as (D90-D10) / D50 (again, unless otherwise specified, each D value is based on volume).

[0029] This can be achieved by using Malvern Mastersizer TM 3000 light scattering techniques or optical digital microscopy analysis are used to determine particle size. Unless otherwise specified, light scattering techniques are used for particle size analysis.

[0030] For light scattering technology, the control sample is Quality Audit Standards QAS4002 (trade name). TM Glass microspheres with diameters ranging from 15 μm to 150 μm were purchased from Malvern Analytical Ltd. Unless otherwise specified, samples were analyzed in dry powder form. An AERO S dry powder dispersion module with a MasterSizer was used. TM The 3000 particles were dispersed in air and analyzed. The particle size was determined using instrument software based on a graph showing the change in bulk density as a function of size.

[0031] Particle size measurements and diameter span can also be determined using optical digital microscopy. Optical images were obtained using a Keyence VHX-2000 digital microscope and software version 2.3.5.1 for particle size analysis (system version 1.93).

[0032] As used in this article, when referring to sieving, the aperture / sieve size is described according to the American standard sieve (ASTM E11-17).

[0033] As used herein, the terms "roundness" and "sphericity" relative to particles refer to how closely a particle approximates a perfect sphere. To determine roundness, optical microscopic images of the particles are taken. The perimeter (P) and area (A) of the particle in the plane of the microscopic image are calculated (e.g., using a SYSMEX FPIA 3000 particle shape and size analyzer, available from Malvern Instruments). The roundness of the particle is C. EA / P, where C EA It is the circumference of a circle whose area is equal to the area (A) of the actual particle.

[0034] As used in this article, the term "shear" refers to stirring or similar processes that cause mechanical agitation in a fluid.

[0035] As used in this article, the term "aspect ratio" refers to the length divided by the width, where the length is greater than the width.

[0036] Unless otherwise specified, the melting point of the polymer shall be determined by ASTM E794-06 (2018) with a ramp rate and cooling rate of 10 °C / min.

[0037] Unless otherwise specified, the softening temperature or softening point of the polymer shall be determined according to ASTM D6090-17. The softening temperature may be measured using a cup-ball apparatus available from Mettler-Toledo, with a 0.50 g sample and a heating rate of 1 °C / min.

[0038] The angle of repose is a measure of the flowability of powder. The angle of repose was determined using the Hosokawa Micron PT-R powder property tester, according to ASTM D6393-14, "Standard Test Method for Bulk Solids Characterized by Carr Indices".

[0039] Hausner ratio (H r ) is a measure of the flowability of powder, and is determined by H r= ρ_compacted / ρ_packed, where ρ_packed is the packing density according to ASTM D6393-14, and ρ_compacted is the compacted density according to ASTM D6393-14.

[0040] As used herein, unless otherwise specified, the viscosity of the carrier fluid is the kinematic viscosity at 25°C, measured according to ASTM D445-19. For commercially available carrier fluids (e.g., PDMS oil), the kinematic viscosity data cited herein are provided by the manufacturer, regardless of whether they were measured according to the aforementioned ASTM or another standard measurement technique.

[0041] Thermoplastic polymer particles containing light absorbers (OACTP particles) and their preparation method

[0042] The methods and compositions described herein relate to OACTP particles. The light absorber in the particles is non-covalently bonded (e.g., via hydrogen bonds, ionic bonds, and / or π-π stacking of aromatic polymers and fluorophores) to the polymer. The light absorber may associate with the polymer during and / or after particle formation. The particles described herein (before and / or after incorporation of the light absorber) are formed by melt emulsification. In a non-limiting example method, the light absorber and polymer may be mixed before and / or during melt emulsification. Without being limited by theory, it is believed that in such methods, the light absorber is non-covalently bonded to the polymer throughout the particle. As an alternative or supplement to the foregoing, particles may be formed by melt emulsification followed by exposure to the light absorber (e.g., immersion in an ethanol solution of the light absorber and / or washing with an ethanol solution of the light absorber). Without being limited by theory, it is believed that in such methods, the light absorber is non-covalently bonded to the polymer on or near the particle surface.

[0043] Figure 1 This is a flowchart of a non-limiting example method 100 of this disclosure. A thermoplastic polymer 102, a carrier fluid 104, an optional emulsion stabilizer 106, and an optional light absorber 108 are combined 110 to produce a mixture 112. Components 102, 104, 106, and 108 may be added in any order and include mixing and / or heating during the process of combining components 102, 104, 106, and 108 in 110.

[0044] The mixture 112 is then processed by applying sufficiently high shear to the mixture 112 at a temperature greater than the melting or softening temperature of the thermoplastic polymer 102 to form a melt emulsion 116. Since the temperature is above the melting or softening temperature of the thermoplastic polymer 102, the thermoplastic polymer 102 becomes a polymer melt. The shear rate should be high enough to disperse the polymer melt in droplets (i.e., polymer emulsion 116) in the carrier fluid 104. Without being theoretically limited, it is believed that, all other things being equal, increasing the shear should reduce the size of the polymer melt droplets in the carrier fluid 104. However, at some point, increasing the shear and reducing the droplet size may have a diminishing return, and / or may result in damage to the droplet contents, thereby reducing the quality of the particles thus prepared.

[0045] The molten emulsion 116 inside and / or outside the mixing container is then cooled to allow the polymer droplets to solidify into thermoplastic polymer particles (also known as solidified thermoplastic polymer particles). When the light absorber 108 is included in the mixture 112, the thermoplastic polymer particles 124 are OACTP particles.

[0046] The cooled mixture 120 can then be processed 122 to separate the thermoplastic polymer particles 124 from other components 126 (e.g., carrier fluid 104, excess emulsion stabilizer 106, etc.) and to wash or otherwise purify the thermoplastic polymer particles 124. The thermoplastic polymer particles 124 comprise (a) a thermoplastic polymer 102, (b) when included, a light absorber 108, and (c) when included, at least a portion of an emulsion stabilizer 106 coated on the outer surface of the thermoplastic polymer particles 124. The emulsion stabilizer 106 or a portion thereof may be deposited as a uniform coating on the thermoplastic polymer particles 124. Depending on non-limiting factors such as temperature (including cooling rate), the type of thermoplastic polymer 102, and the type and size of the emulsion stabilizer 106, nanoparticles of the emulsion stabilizer 106 may be at least partially embedded within the outer surface of the thermoplastic polymer particles 124 during association with the outer surface of the thermoplastic polymer particles 124. Even without intercalation, the nanoparticles within the emulsion stabilizer 106 can maintain robust association with the thermoplastic polymer particles 124 to facilitate their further use. In contrast, dry mixing already formed thermoplastic polymer microparticles (e.g., formed by cryogenic milling or precipitation processes) with a flow aid (such as silica nanoparticles) does not produce a robust, uniform coating of the flow aid on the thermoplastic polymer microparticles.

[0047] The thermoplastic polymer particles 124 can be further purified 128 (described in more detail below) to produce purified thermoplastic polymer particles 130. Regardless of whether the light absorber 108 is included in the mixture 112, the light absorber 132 can be applied 134 to the thermoplastic polymer particles 124 / 130 to produce OACTP particles 136.

[0048] This example method 100 illustrates including a light absorber 108 in a mixture 112 and applying another light absorber 132 134 to thermoplastic polymer particles 124 / 130 (which are OACTP particles due to the inclusion of light absorber 108). The light absorber 108 and the additional light absorber 132 may have the same or different compositions. In an alternative method not shown, only one of the following may be performed: (a) including light absorber 108 in the mixture 112, and (b) applying light absorber 132 134 to the thermoplastic polymer particles 124 / 130.

[0049] Thermoplastic polymer 102 and carrier fluid 104 should be selected such that they are immiscible at various processing temperatures (e.g., from room temperature to processing temperature). An additional factor to consider is the viscosity difference (e.g., variation or ratio) between the molten thermoplastic polymer 102 and carrier fluid 104 at the processing temperature. Viscosity differences can affect droplet breakup and particle size distribution. Without being theoretically limited, it is believed that when the viscosities of the molten thermoplastic polymer 102 and carrier fluid 104 are too similar, the roundness of the product as a whole can be reduced, with particles becoming more oval and exhibiting a more elongated structure.

[0050] The thermoplastic polymer 102 shall include at least one polymer capable of non-covalent bonding (e.g., via hydrogen bonding, ionic bonding, and / or π-π stacking) to a light absorber. Generally, such polymers include portions such as alcohols, ethers, carboxylic acids, esters, amines, amides, fluorides, sulfoxides, aryl rings (in the main chain and / or side chains of the main chain), and any combination thereof. Examples of thermoplastic polymers capable of non-covalently bonding to light absorbers include, but are not limited to, polyamides, polyurethanes, polyacetals, polycarbonates, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyesters (e.g., polylactic acid), polyethers, polyethersulfones, polyetheretherketones, polyacrylates, polymethacrylates, polyimides, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide, vinyl polymers, polyaryl ethers, polyaryl sulfides, polyetherketones, polyamide-imides, polyetherimides, polyether esters, copolymers comprising polyether blocks and polyamide blocks (PEBA or polyether block amides), grafted or ungrafted thermoplastic polyolefins, functionalized or unfunctionalized ethylene / vinyl monomer polymers, and so on. Functionalized or unfunctionalized ethylene / (meth)acrylate alkyl esters, functionalized or unfunctionalized (meth)acrylate polymers, functionalized or unfunctionalized ethylene / vinyl monomer / (meth)acrylate alkyl ester terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / (meth)acrylate alkyl ester / carbonyl terpolymers, methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene / vinyl acetate), polyisoprene, styrene-based block copolymers, polyacrylonitrile, organosilicon, etc., and any combination thereof. Copolymers containing one or more of the foregoing substances may also be used in the methods and systems disclosed herein. For example, copolymers of polyolefins (e.g., polyethylene, polypropylene) and / or polybutadiene with one or more of the above examples of thermoplastic polymers capable of non-covalent bonding to light absorbers.

[0051] In addition, other thermoplastic polymers that do not form hydrogen bonds and / or ionic bonds with the light absorber may be blended with polymers that do form hydrogen bonds and / or ionic bonds. Examples of polymers that may be included, besides thermoplastic polymers capable of forming hydrogen bonds and / or ionic bonds, include, but are not limited to, polyolefins (e.g., polyethylene, polypropylene), polybutadiene, and any combinations thereof.

[0052] The thermoplastic polymers in the compositions and methods disclosed herein may be elastomers or non-elastomers. Some of the other thermoplastic polymers mentioned above may be elastomers or non-elastomers, depending on the exact composition of the polymer. For example, polyethylene, as a copolymer of ethylene and propylene, may be elastomers and this is not dependent on the amount of propylene in the polymer.

[0053] Thermoplastic elastomers generally fall into one of six categories: styrene-based block copolymers, thermoplastic polyolefin elastomers, thermoplastic vulcanizates (also known as elastomer alloys), thermoplastic polyurethanes, thermoplastic copolyesters, and thermoplastic polyamides (usually block copolymers containing polyamides). Examples of thermoplastic elastomers can be found in the following literature: *Handbook of Thermoplastic Elastomers*, 2nd edition, edited by BMWalker and CPRander, Van Nostrand Reinhold, New York, 1988. Examples of thermoplastic elastomers include, but are not limited to, elastic polyamides, polyurethanes, copolymers containing polyether blocks and polyamide blocks (PEBA or polyether block amides), methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, polybutadiene, polyisoprene, styrene-based block copolymers, and polyacrylonitrile, silicone, etc. Elastic styrene-based block copolymers may include at least one block selected from isoprene, isobutene, butene, ethylene / butene, ethylene-propylene, and ethylene-ethylene / propylene. More specific examples of elastic styrene-based block copolymers include, but are not limited to, poly(styrene-ethylene / butene), poly(styrene-ethylene / butene-styrene), poly(styrene-ethylene / propylene), poly(styrene-ethylene / propylene-styrene), poly(styrene-ethylene / propylene-styrene-ethylene-propylene), poly(styrene-butadiene-styrene), poly(styrene-butene-butadiene-styrene), and any combination thereof.

[0054] Examples of polyamides include, but are not limited to, polycaprolactam (nylon 6, polyamide 6, or PA6), poly(hexamethylene succinate) (nylon 4,6, polyamide 4,6, or PA4,6), polyhexamethylene adipamide (nylon 6,6, polyamide 6,6, or PA6,6), polypentyl hexamethylene adipamide (nylon 5,6, polyamide 5,6, or PA5,6), polyhexamethylene sebacate (nylon 6,10, polyamide 6,10, or PA6,10), polyundecanoamide (nylon 11, polyamide 11, or PA11), polydodecanoamide (nylon 12, polyamide 12, or PA12), and polyhexamethylene terephthalamide (nylon 6T, polyamide 6T, or PA6T). Nylon 10,10 (polyamide 10,10 or PA10,10), Nylon 10,12 (polyamide 10,12 or PA10,12), Nylon 10,14 (polyamide 10,14 or PA10,14), Nylon 10,18 (polyamide 10,18 or PA10,18), Nylon 6,18 (polyamide 6,18 or PA6,18), Nylon 6,12 (polyamide 6,12 or PA6,12), Nylon 6,14 (polyamide 6,14 or PA6,14), Nylon 12,12 (polyamide 12,12 or PA12,12), semi-aramids, aramids (aramid fibers), and any combination thereof. Copolyamides may also be used. Examples of copolyamides include, but are not limited to, PA 11 / 10,10, PA 6 / 11, PA 6,6 / 6, PA 11 / 12, PA 10,10 / 10,12, PA 10,10 / 10,14, PA 11 / 10,36, PA 11 / 6,36, PA 10,10 / 10,36, PA 6T / 6,6, and any combination thereof. Examples of polyamide elastomers include, but are not limited to, polyesteramides, polyether esteramides, polycarbonate-esteramides, and polyether-block-amide elastomers. In this document, a polyamide followed by a single quantity is a polyamide having that quantity of main-chain carbon between each nitrogen atom. A polyamide followed by a first quantity followed by a comma and a second quantity is a polyamide having a first quantity of main-chain carbon between nitrogen atom for segments without side groups =O and a second quantity of main-chain carbon between two nitrogen atom for segments with side groups =O. As a non-limiting example, nylon 6,10 is [NH-(CH2)6-NH-CO-(CH2)8-CO]. n The quantity of polyamide followed by a backslash indicates the quantity of the polyamide copolymer before and after the backslash.

[0055] Examples of polyurethanes include, but are not limited to, polyether polyurethanes, polyester polyurethanes, blends of polyether and polyester polyurethanes, and any combinations thereof. Examples of thermoplastic polyurethanes include, but are not limited to, poly[4,4′-methylenebis(phenyl isocyanate)-alternating-1,4-butanediol / di(propylene glycol) / polycaprolactone], 1190A (a polyether polyurethane elastomer, available from BASF) 1190A10 (a polyether polyurethane elastomer, available from BASF) and any combination thereof.

[0056] When using more than one thermoplastic polymer, compatibilizers may optionally be used to improve the blending efficiency and effectiveness of the thermoplastic polymers. Examples of polymer compatibilizers include, but are not limited to, PROPOLDER. TM MPP2020 20 (Polypropylene, available from Polygroup Inc.), PROPOLDER TM MPP2040 40 (Polypropylene, available from Polygroup Inc.) and NOVACOM TM HFS2100 (maleic anhydride-functionalized high-density polyethylene polymer, available from Polygroup Inc.) and KEN-REACT TM CAPS TM L TM 12 / L (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM CAPOW TM L TM 12 / H (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM LICA TM 12 (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM CAPS TM KPR TM 12 / LV (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM CAPOW TM KPR TM 12 / H (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM Titanates and zirconates (organometallic coupling agents, available from Kenrich Petrochemicals), VISTAMAXX TM(Ethylene-propylene copolymer, available from ExxonMobil), SANTOPRENE TM (Ethylene propylene diene monomer (EPDM) and polypropylene thermoplastic vulcanizates are available from ExxonMobil and Vistalon.) TM (EPDM rubber, available from ExxonMobil) and EXACT TM (Plastic material, available from ExxonMobil) TM (Polymer resin, available from ExxonMobil) FUSABOND TM M603 (random ethylene copolymer, available from Dow Chemical Company (DOW)) and FUSABOND TM E226 (anhydride-modified polyethylene, available from Dow Chemical Company (DOW)), BYNEL TM 41E710 (co-extrudeable adhesive resin, available from Dow Chemical Company (DOW)), SURLYN TM 1650 (ionomer resin, available from Dow Chemical Company (DOW)), FUSABOND TM P353 (a chemically modified polypropylene copolymer, available from Dow Chemical Company (DOW)) and ELVALOY TM PTW (ethylene terpolymer, available from Dow Chemical Company (DOW)) and ELVALOY TM 3427AC (a copolymer of ethylene and butyl acrylate, available from Dow Chemical Company (DOW)) and LOTADER TM AX8840 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 3210 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 3410 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 3430 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 4700 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM AX8900 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM4720 (a terpolymer based on ethylene-acrylate, available from Arkema), BAXXODUR TM EC 301 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 311 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 303 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 280 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 201 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 130 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 110 (an amine for epoxy resins, available from BASF), styrene, polypropylene, polyamide, polycarbonate, EASTMAN TM G-3003 (a maleic anhydride-grafted polypropylene, available from Eastman), RETAIN TM (Polymer modifier, available from Dow Chemical Company (DOW)), AMPLIFY TY TM (Maleic anhydride grafted polymer, available from Dow Chemical Company (DOW) and INTUNE) TM (olefin block copolymers, available from Dow Chemical Company (DOW)) and any combination thereof.

[0057] The thermoplastic polymer 102 may have a melting point or softening temperature of about 50°C to about 450°C (or about 50°C to about 125°C, or about 100°C to about 175°C, or about 150°C to about 280°C, or about 200°C to about 350°C, or about 300°C to about 450°C).

[0058] Thermoplastic polymer 102 may have a glass transition temperature of about -50°C to about 400°C (or about -50°C to about 0°C, or about -25°C to about 50°C, or about 0°C to about 150°C, or about 100°C to about 250°C, or about 150°C to about 300°C, or about 200°C to about 400°C) (derived according to ASTM E1356-08 (2014) with a ramp rate and cooling rate of 10°C / min).

[0059] Thermoplastic polymer 102 may optionally contain an additive. Typically, this additive is present before thermoplastic polymer 102 is added to mixture 112. Therefore, the additive is dispersed throughout the thermoplastic polymer in the thermoplastic polymer melt droplets and the resulting thermoplastic polymer particles. Therefore, for clarity, this additive is referred to herein as an "internal additive." The internal additive can be blended with the thermoplastic polymer either just before the preparation of mixture 112 or well in advance.

[0060] When describing the component amounts in the compositions described herein (e.g., mixture 112 and thermoplastic polymer particles 124), the weight percentage of thermoplastic polymer 102 does not include internal additives. For example, a composition containing 1% emulsion stabilizer is a composition containing 0.9g emulsion stabilizer, 90g thermoplastic polymer, and 10g internal additives, based on 100g of thermoplastic polymer 102 comprising 10% internal additives and 90% thermoplastic polymer.

[0061] Internal additives may be present in the thermoplastic polymer 102 in an amount of about 0.1% to about 60% by weight (or about 0.1% to about 5% by weight, or about 1% to about 10% by weight, or about 5% to about 20% by weight, or about 10% to about 30% by weight, or about 25% to about 50% by weight, or about 40% to about 60% by weight). For example, the thermoplastic polymer 102 may comprise about 70% to about 85% by weight of the thermoplastic polymer and about 15% to about 30% by weight of internal additives, such as glass fiber or carbon fiber.

[0062] Examples of internal additives include, but are not limited to, fillers, reinforcing agents, pigments, pH adjusters, and combinations thereof. Examples of fillers include, but are not limited to, glass fibers, glass particles, mineral fibers, carbon fibers, oxide particles (e.g., titanium dioxide and zirconium dioxide), metal particles (e.g., aluminum powder), and any combination thereof. Examples of pigments include, but are not limited to, organic pigments, inorganic pigments, carbon black, and any combination thereof.

[0063] The thermoplastic polymer 102 may be present in the mixture 112 in a proportion of about 5% to about 60% by weight (or about 5% to about 25% by weight, or about 10% to about 30% by weight, or about 20% to about 45% by weight, or about 25% to about 50% by weight, or about 40% to about 60% by weight) of the thermoplastic polymer 102 and the fluid carrier 104.

[0064] The suitable carrier fluid 104 has a viscosity of about 1,000 cSt to about 150,000 cSt (or about 1,000 cSt to about 60,000 cSt, or about 40,000 cSt to about 100,000 cSt, or about 75,000 cSt to about 150,000 cSt) at 25°C.

[0065] Examples of carrier fluid 104 include, but are not limited to, silicone oil, fluorinated silicone oil, perfluorinated silicone oil, polyethylene glycol, alkyl-terminated polyethylene glycol (e.g., C1-C4 terminal alkyl, such as tetraethylene glycol dimethyl ether (TDG)), alkanes, liquid petrolatum, vison oil, turtle oil, soybean oil, perhydrosqualene, sweet almond oil, calophyllum oil, palm oil, parleam oil, grapeseed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, almond oil, castor oil, avocado oil, jojoba oil, olive oil, cereal germ oil, esters of lanolic acid, esters of oleic acid, esters of lauric acid, esters of stearic acid, fatty acid esters, higher fatty acids, fatty alcohols, polysiloxanes modified with fatty acids, polysiloxanes modified with fatty alcohols, polysiloxanes modified with polyoxyethylene, and any combination thereof. Examples of silicone oils include, but are not limited to, polydimethylsiloxane, methylphenyl polysiloxane, alkyl-modified polydimethylsiloxane, alkyl-modified methylphenyl polysiloxane, amino-modified polydimethylsiloxane, amino-modified methylphenyl polysiloxane, fluorinated polydimethylsiloxane, fluorinated methylphenyl polysiloxane, polyether-modified polydimethylsiloxane, polyether-modified methylphenyl polysiloxane, and any combination thereof. When the carrier fluid 104 contains two or more of the above substances, the carrier fluid 104 may have one or more phases. For example, a single-phase carrier fluid 104 can be formed by a fatty acid-modified polysiloxane and a fatty alcohol-modified polysiloxane (preferably the fatty acid and fatty alcohol have similar chain lengths). In another example, a carrier fluid 104 containing silicone oil and polyethylene glycol with alkyl terminals can form a two-phase carrier fluid 104.

[0066] The carrier fluid 104 may be present in the mixture 112 in a proportion of about 40% to about 95% by weight (or about 75% to about 95% by weight, or about 70% to about 90% by weight, or about 55% to about 80% by weight, or about 50% to about 75% by weight, or about 40% to about 60% by weight) of the thermoplastic polymer 102 and the carrier fluid 104.

[0067] In some cases, the carrier fluid 104 may have a concentration of approximately 0.6 g / cm³. 3 Approximately 1.5 g / cm³ 3 The density of thermoplastic polymer 102 is approximately 0.7 g / cm³. 3 Approximately 1.7 g / cm³3 The density of thermoplastic polymers is similar to, lower than or higher than that of the fluid carrier.

[0068] The light absorber 108 / 132 should be selected to be non-covalently bonded to the thermoplastic polymer 102. Furthermore, if the light absorber 108 is included in the mixture 112, the light absorber 108 should be sufficiently stable to not decompose at the processing temperature 114.

[0069] Light absorbers 108 / 132 may be derived from the following known families, including but not limited to: rhodamine, fluorescein, coumarin, naphthalenedicarboximide, benzoxanthracene, acridine, cyanine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polyacetylenes, triarylmethane, anthraquinone, pyrazolone, quinophthalone, carbonyl dyes, diazo dyes, cyclic ketones, pyrrolopyrroledione (DPP), dioxazine dyes, phthalocyanine, indigoanthraquinone, benzoanthraquinone, violetanthraquinone, azo dyes, phthalocyanine dyes, quinacridone dyes, anthraquinone dyes, indigo dyes, thio-indigo dyes, pyrenone dyes, dinaphthalene-phenylene dyes, isoindole dyes, aromatic amino acids, flavins, pyridoxine derivatives, chlorophyll derivatives, and any combination thereof. Specific examples of light absorbers 108 / 132 include, but are not limited to, DPP derivatives (e.g., DPP-PhCO; DPP-PhCN; DPP-NaCO and DPP-NaCN); 9-aminoacridine; 9H-1,8-diazafluorene-9-one (DFO); 2-aminoacridineone; halogen (NSC 12097); calcein blue; fluorescein; 5(6)-carboxyfluorescein; 5(6)-carboxyfluorescein-N-hydroxysuccinimide ester; [9-(2-ethoxycarbonylphenyl)-6-(ethylamino)-2,7-dimethylxanthanyl-3-ylidene]-ethylammonium chloride (also known as Rhodamine 6G and Basic Red 1); [9-(2-carboxyphenyl)-6-diethylamino-3-xanthanyl]-diethylammonium chloride (also known as Rhodamine 610 and Basic Violet 10) ); [6-(diethylamino)-9-(2-ethoxycarbonylphenyl)xanthon-3-ylidene]-diethylammonium chloride (also known as Basic Violet 11); N,N-diethyl-4-[(E)-2-(1,3,3-trimethylindol-1-onth-2-yl)vinyl]aniline chloride (also known as Basic Violet 16); 7-(diethylamino)-3-(1,3-dimethylbenzimidazol-3-onth-2-yl)benzopyran-2-one chloride (also known as Basic Yellow 4) 0); 6-amino-2-(2,4-dimethylphenyl)benzo[de]isoquinoline-1,3-dione (also known as Solvent Yellow 44); 4-amino-N-2,4-dimethyl-1,8-naphthalenediamide (also known as Solvent Yellow 135); Pigment Violet 19; 1,4-bis(4-tert-butylphenyl)-3-hydroxy-2H-pyrrolo[3,4-c]pyrrolo-6-one (also known as Pigment Orange 73); 1,2-dihydroxyanthraquinone (also known as alizarin); Carmine Red acid; 1,3-dihydroxyanthraquinone; 1,4-dihydroxyanthraquinone; 1-hydroxy-4-(p-tolylamino)anthraquinone (also known as oil violet and solvent violet 13); 1,8-dihydroxy-3-methoxy-6-methylanthraquinone (also known as emodin methyl ether); 1,2,5-trihydroxy-6-methylanthraquinone-9,10-dione (also known as mulberry ketone); calcein (also known as fluorescein); 6-carboxyfluorescein succinimide ester; 6-carboxyfluorescein (also known as 6-FAM);2',7'-Dichloro-3',6'-Dihydroxy-3H-spiro[2-benzofuran-1,9'-xanthon]-3-one (also known as dichlorofluorescein); fluorescein isothiocyanate; 4',5'-dibromofluorescein; 5(6)-carboxy-2',7'-dichlorofluorescein; 2-pyrenepropionic acid; 2-perylpropionic acid; 3,9-dinaphthalene-phenylenediic acid; 4-dimethylaminobenzaldehyde; (9H-pyrene[4,5-d]imidazol-10-yl)-benzaldehyde; phenylalanine; tryptophan; tyrosine; unsubstituted metal phthalocyanine; aluminum phthalocyanine; polychlorophthalocyanine aluminum; antimony phthalocyanine; barium phthalocyanine; beryllium phthalocyanine; hexachlorophthalocyanine cadmium; cadmium phthalocyanine; calcium phthalocyanine; cerium phthalocyanine; chromium phthalocyanine; cobalt phthalocyanine; cobalt chlorophthalocyanine ; 4-Aminophthalocyanine copper; Bromochlorophthalocyanine copper; 4-Chlorophthalocyanine copper; 4-Nitrophthalocyanine copper; Phthalocyanine copper; Polychlorophthalocyanine copper; Deuterated phthalocyanine; Dysprosium phthalocyanine; Erbium phthalocyanine; Europium phthalocyanine; Gadolinium phthalocyanine; Gallium phthalocyanine; Germanium phthalocyanine; Hafnium phthalocyanine; Halogen-substituted metal phthalocyanine; Holmium phthalocyanine; Indium phthalocyanine; Iron phthalocyanine; Polyhalogenated iron phthalocyanine; Lanthanum phthalocyanine; Phenylphthalocyanine; Lithium phthalocyanine; Lutene phthalocyanine; Magnesium phthalocyanine; Manganese phthalocyanine; Mercuric phthalocyanine; Molybdenum phthalocyanine; Neodymium phthalocyanine; Nickel phthalocyanine; Polyhalogenated nickel phthalocyanine; Osmium phthalocyanine; Palladium phthalocyanine; Chlorophthalocyanine palladium; Alkoxy metal phthalocyanine; Alkylamino metal phthalocyanine; Alkyl mercaptophthalocyanine; Arylalkylamino metal phthalocyanine; Aryloxy metal phthalocyanine; Aryl mercaptophthalocyanine; Piperidine copper phthalocyanine; Cycloalkylamino metal phthalocyanine; Dialkylamino Benzyl phthalocyanine; Diarylalkylamino phthalocyanine; Dichloroalkylamino phthalocyanine; Hexadecyl phthalocyanine; Iminomethyl phthalocyanine; Octaazametal phthalocyanine; Tetraazametal phthalocyanine; Tetra-4-acetamidometal phthalocyanine; Tetra-4-aminobenzoyl phthalocyanine; Tetra-4-amino phthalocyanine; Tetrachloromethyl phthalocyanine; Tetradiazomethyl phthalocyanine; Tetra-4,4-dimethyloctaazametal phthalocyanine; Tetra-4,5-diphenyloctaazametal phthalocyanine; Tetra-(6-methylbenzothiazolyl) phthalocyanine; Tetra-p-methylphenylamino phthalocyanine; Tetramethyl phthalocyanine; Tetranaphthotriazolyl phthalocyanine; Tetra-4-naphthyl phthalocyanine; Tetra-4-nitro phthalocyanine; Tetra-zonaphthyl-4 ,5-Octaazametal phthalocyanine; Tetra-2,3-phenylene oxide metal phthalocyanine; Tetra-4-phenyloctaazametal phthalocyanine; Tetraphenyl metal phthalocyanine; Tetrapyridyl metal phthalocyanine; Tetra-4-trifluoromethyl mercaptophthalocyanine; Tetra-4-trifluoromethyl metal phthalocyanine; 4,5-thionaphthalene octaazametal phthalocyanine; Platinum phthalocyanine; Potassium phthalocyanine; Rhodium phthalocyanine; Samarium phthalocyanine; Silver phthalocyanine; Silicon phthalocyanine; Sodium phthalocyanine; Thorium phthalocyanine; Thulium phthalocyanine; Tin phthalocyanine; Tin phthalocyanine; Titanium phthalocyanine; Uranium phthalocyanine; Vanadium phthalocyanine; Vanadyl phthalocyanine; Ytterbium phthalocyanine; Zinc phthalocyanine; Zinc phthalocyanine; N-(9,10-dioxoanthracene-1-yl)-7-oxobenzo[e]naphthalene intercalation diazabenzyl-4-carboxamide (also known as anthraquinone yellow and pigment yellow 108);4-Chloro-3-[(2Z)-2-[1-[5-chloro-4-[[(2Z)-2-[[2-chloro-5-[N-[2-(4-chlorophenoxy)-5-(trifluoromethyl)phenyl]-C-hydroxycarbonimide]phenyl]hydrazine]-3-oxobutyryl]amino]-2-methylaniline]-1,3-dioxobutyryl]hydrazine]-N-[2-(4-chlorophenoxy)-5-(trifluoro] [Methyl)phenyl]phenylcarboxyimide acid (also known as diazo yellow GG and pigment yellow 128); 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridin-7,14-dione (also known as quinacridone magnesium Y and pigment red 122); (1Z,11Z,19Z,29Z)-2,11,20,29-tetraaza-37,38,39,40-tetraazanonacyclo[28.6.1.1; 3,10 .1 12, 19 .1 21,28 .0 4,9 .0 13,18 .0 22,27 .0 31,36 [Tetradecane-1,3,5,7,9,11,13,15,17,19,21,23,25,27,29,31,33,35-octadecenecopper (also known as Phthalocyanine Blue β and Pigment Blue 15:3); (1Z,11Z,19Z,29Z)-2,11,20,29-tetraaza-37,38,39,40-tetraazanonacyclo[28.6.1.1] 3,10 .1 12,19 .1 21,28 .0 4,9 .0 13,18 .0 22,27 .0 31,36[Tetradecane-1,3,5,7,9,11,13,15,17,19,21,23,25,27,29,31,33,35-octadecenecopper (also known as Phthalocyanine Blue α and Pigment Blue 15:2); 2-[(3-carboxy-2-oxynaphth-1-yl)diazepinel]-4-chloro-5-methylbenzenesulfonate calcium (also known as Permanent Red 2B (calcium) and Pigment Red 48:2); 2,9-dichloro-5,12-dihydroquinolino[2,3-b]acridin-7,14-dione (also known as quinacridone magnesium B and Pigment Red 202); 4,5-dichloro-2-[[5-methyl-3-oxo-2-(3-sulfophenyl)-1H] -pyrazol-4-yl]diazenin]benzenesulfonic acid (also known as Yellow 183); 2-[[2-chloro-4-[3-chloro-4-[[1-(4-chloro-2,5-dimethoxyaniline)-1,3-dioxabut-2-yl]diazenin]phenyl]phenyl]diazenin]-N-(4-chloro-2,5-dimethoxyphenyl)-3-oxobutyramide (also known as diaryl yellow and pigment yellow 83); 2-[(3-carboxy-2-oxynaphthyl-1-yl)diazenin]-4-chloro-5-methylbenzenesulfonic acid disodium salt (also known as Wachtung Red B and pigment red 48); 3,10,17,24-tetraazapentacyclo[13.13.2.0] 2, 10 .0 4,9 .0 12,29 .0 16,24 .0 18,23 .0 26,30 [Triacontane-1(29),2,4,6,8,12,14,16,18,20,22,26(30),27-tetracene-11,25-dione (also known as chondrine orange and pigment orange 43); 4,5,6,7-tetrachloro-3-[4-[(4,5,6,7-tetrachloro-3-oxoisoindole-1-yl)amino]phenyl]iminoisoindole-1-one (also known as tetrachloroisoindolelinone yellow R and pigment yellow 110); 7,18-dioxane-7-cyclo[14.6.2.2] 2,5 .0 3,12 .0 4,9 .0 13,23 .0 20,24 [Hexacosane-1(23),2,4,9,11,13,15,20(24),21,25-decaen-6,8,17,19-tetraone (also known as perylene red Y and pigment red 224); 7,18-dimethyl-7,18-diazaheptacyclo[14.6.2.2] 2,5 .0 3,12 .0 4,9 .0 13,23 .0 20,24Hexacosane-1(23),2,4,9,11,13,15,20(24),21,25-decaen-6,8,17,19-tetraone (also known as pyrene red and pigment red 179); (2Z)-1,3,3-trimethyl-2-[(E)-3-(1,3,3-trimethylindole-1-onth-2-yl)prop-2-enyl]indole chloride (also known as basic red 12); tricyanine dye; hemicyanine dye; 2,4-dimethoxy-N-[(E)-2-(1,3,3-trimethylindole-1-onth-2-yl)prop-2-enyl]indole chloride (also known as basic red 12); tricyanine dye; hemicyanine dye; 2,4-dimethoxy-N-[(E)-2-(1,3,3-trimethylindole-1-onth-2-yl)prop-2-yl]indole chloride -1-On-2-yl)vinyl]aniline chloride (also known as Basic Yellow 11), cyanine-like dyes; 4-[3-methyl-4-[(1E,3E,5Z)-5-[3-methyl-5-oxo-1-(4-sulfophenyl)pyrazol-4-ylidene]pent-1,3-dienyl]-5-oxo-4H-pyrazol-1-yl]benzenesulfonic acid (also known as cyanine-like 805 Blue), styrene-based dyes; 17-(3-methoxypropyl)-11,16,18-trioxo-3,10,17-triazahexane[13.6.2.0] 2,10 .0 4,9 .0 12,22 .0 19,23[Tridecane-1(21),2,4,6,8,12(22),13,15(23),19-Nonen-20-carboxynitrile (also known as Disperse Yellow 31); diarylmethimide dyes; triarylmethimide dyes; [4-[[4-(dimethylamino)phenyl]-phenylmethylene]cyclohexyl-2,5-diene-1-ylidene]-dimethylammonium chloride (also known as Basic Green 4 and Malachite Green); [4-[bis[4-(dimethylamino)phenyl]methylene]cyclohexyl-2,5-diene-1-ylidene]-dimethylammonium chloride (also known as Basic Violet) 3 and Crystal Violet); aziridine analogues, methine dyes; 4-methoxy-N-methyl-N-[(E)-(1,3,3-trimethylindol-1-onthiol-2-yl)methyleneamino]aniline methyl sulfate (also known as Basic Yellow 28), diazahexacyanine dyes; 4-[(2,4-dimethyl-1,2,4-triazol-4-onthiol-3-yl)diazeninyl]-N,N-dimethylaniline methyl sulfate (also known as Basic Red 22); 2-[N-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazo-3-onthiol-2-yl)di] Methyl ethanol sulfate [[4-aminophenyl]phenylamino]ethanol (also known as Basic Blue 41); methyl violet dye; magenta dye; 4-[(4-aminophenyl)-(4-iminocyclohex-2,5-dien-1-yl)methyl]aniline hydrochloride (also known as pararosaniline and Basic Red 9); phenol dye; 3,3-bis(4-hydroxyphenyl)-2-benzofuran-1-one (also known as phenolphthalein); malachite green dye; 2-[[4-[ethyl-[(3-sulfonylphenyl)methyl]amino]phenyl]-[4-[ethyl-[(3-sulfonylphenyl)methyl]aza] [Imide]cyclohexyl-2,5-diene-1-ylidene]methyl]benzenesulfonate disodium (also known as Brilliant Blue FCF), Victoria Blue dye; [4-[bis[4-(dimethylamino)phenyl]methylene]naphthalene-1-ylidene]ethyl azirconium chloride (also known as Victoria Blue R); xanthonium dye; 9,10-anthraquinone; 1-nitroanthraquinone; anthraquinone-1-sulfonic acid; dinitroanthraquinone; 4,8-diamino-1,5-dihydroxy-9,10-dioxoanthracene-2-sulfonate sodium (also known as Acid Blue 43); 19,33-dichlorononacyclo[18.10.2.2] 2,5 .0 3,16 .0 4,13 .0 6,11 .0 17,31 .0 21,26 .0 28,32[Tetradecane-1(31),2(34),3(16),4(13),5(33),6,8,10,14,17,19,21,23,25,28(32),29-hexadecene-12,27-dione (also known as Reduction Violet 1); 1-Amino-4-hydroxy-2-phenoxyanthracene-9,10-dione (also known as Disperse Red 60); N-(24-benzamido-6,13,19,26-tetraoxo-16-azaheptacyclo[15.12.0.0]] 2,15 .0 5,14 .0 7,12 .0 18,27 .0 20,25 [Nonane-1(17),2(15),3,5(14),7(12),8,10,18(27),20(25),21,23,28-dodecane-8-yl)benzamide (also known as Reducing Orange 15); hexacyclic [10.10.2.0] 2,7 .0 9,23 .0 13,18 .0 20,24 [Tetracosane-1(23),2,4,6,9,11,13,15,17,20(24),21-Undecane-8,19-dione (also known as Reduced Yellow 4); 9,18-Dibromohexane [11.7.1.1] 4,20 .0 2 ,11 .0 3,8 .0 17,21Docosane-1(21),2,4,6,8,10,13,15,17,19-decaen-12,22-dione (also known as Reduction Orange 3 and Pigment Red 168); 5-oxo-1-(4-sulfonylphenyl)-4-[(4-sulfonylphenyl)diazeninyl]-4H-pyrazole-3-carboxylic acid trisodium salt (also known as tartrazine); 4-[[5-ethoxycarbonyl-3-oxo-2-(4-sulfonylphenyl)-1H-pyrazole-4-yl]diazeninyl]naphthalene-1-sulfonate (also known as Orange B); 5-chloro-2-hydroxy-3-[(3-methyl-5-oxo-1-phenyl-4H-pyrazole-4-yl)diazeninyl]benzenesulfonate sodium salt (also known as Media Red 19); 2,5-dichloro-4-[3- Methyl-5-oxo-4-[(4-sulfophenyl)diazeninyl]-4H-pyrazol-1-yl]benzenesulfonic acid (also known as Yellow 2G); 2-quinoline-2-ylindene-1,3-dione (also known as Quinoline Yellow); Quinoline orange; 2-(3-hydroxy-1H-indole-2-yl)indole-3-one (also known as Indigo); Sodium 2-[(4-hydroxy-9,10-dioxoanthracene-1-yl)amino]-5-methylbenzenesulfonate (also known as Alizarin Irisol r); 3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-7-[3,4,5-trihydroxy-6-(hydroxymethyl)oxane-2-yl]anthracene-2-carboxylic acid (also known as Carmine); 19,22-dioxanedecyl ring [23.11.1.1] 4,8 .0 2,23 .0 3,18 .0 5,36 .0 9,14 .0 26,31 .0 33,37 .0 16,38 [Octacosane-1(37),2(23),3(18),4(38),5(36),7,9,11,13,15,20,25,27,29,31,33-hexadecene-17,24-dione (also known as Reducing Blue 16); dibromoanthraquinone; 2,20-dichloro-14,32-diethyl-18,36-dioxa-4,14,22,32-tetraazanonane [19.15.0.0] 3,19 .0 5,17 .0 7,15 .0 8,13 .0 23,35 .0 25,33 .0 26,31 [Hexadecane-1,3,5(17),6,8,10,12,15,19,21,23(35),24,26,28,30,33-hexadecene (also known as pigment violet 23); 2,11,20,29,37,38,39,40-octaazanonane [28.6.1.1] 3,10 .1 12,19.1 21,28 .0 4,9 .0 13,18 .0 22,27 .0 31,36 [Tetradecane-1(37),2,4,6,8,10(40),11,13,15,17,19(39),20,22,24,26,28(38),29,31,33,35-eicosene copper (also known as phthalocyanine blue BN); 2,11,20,29,38,40-hexaaza-37,39-diazanonane [28.6.1.1] 3,10 .1 12,19 .1 21,28 .0 4, 9 .0 13,18 .0 22,27 .0 31,36 [Tetracarbamo-1(36),2,4(9),5,7,10(40),11,13,15,17,19,21(38),22(27),23,25,28,30,32,34-nonadecane-6,24-disulfonic acid copper disodium salt (also known as Direct Blue 86); 30,34-dimethoxynonane [18.10.2.2] 2,5 .0 3,16 .0 4,13 .0 6,11 .0 17,31 .0 22,27 .0 28,32 [Tetradecane-1(30),2(34),3(16),4(13),5(33),6,8,10,14,17(31),18,20(32),22,24,26,28-hexadecene-12,21-dione (also known as Reduced Green 1); 30-Nitrosaminotricyclic [18.10.2.2] 2,5 .0 3,16 .0 4,13 .0 6,11 .0 17,31 .0 22,27 .0 28,32 [Tritetradecane-1(30),2,4,6,8,10,13,15,17(31),18,20(32),22,24,26,28,33-hexadecene-12,21-dione (also known as Reduced Green 9); 7,18-bis(4-methoxyphenyl)-7,18-diazaheptacyclo[14.6.2.2] 2,5 .0 3,12 .0 4, 9 .0 13,23 .0 20,24[Hexacosane-1(23),2,4,9,11,13,15,20(24),21,25-Decaene-6,8,17,19-tetraone (also known as Pigment Red 190); 7,18-bis(3,5-dimethylphenyl)-7,18-diazaheptacyclo[14.6.2.2] 2,5 .0 3,12 .0 4, 9 .0 13,23 .0 20,24 [Hexacosane-1(23),2,4,9,11,13,15,20(24),21,25-Decaen-6,8,17,19-tetraone (also known as Pigment Red 149); 7,18-bis(4-phenyldiazeninylphenyl)-7,18-diazaheptacyclo[14.6.2.2] 2,5 .0 3,12 .0 4 ,9 .0 13,23 .0 20,24 [Hexacosane-1(23),2,4,9,11,13,15,20(24),21,25-Decaene-6,8,17,19-tetraone (also known as Pigment Red 178); 7,18-diazaheptacyclo[14.6.2.2] 2,5 .0 3,12 .0 4,9 .0 13,23 .0 20,24 [Hexacosane-1(23),2,4,9,11,13,15,20(24),21,25-decaen-6,8,17,19-tetraone (also known as Pigment Violet 29); 3-(1,3-benzothiazol-2-yl)-7-(diethylamino)benzopyran-2-one (also known as Coumarin 6); 3-(1H-benzimidazol-2-yl)-7-(diethylamino)benzopyran-2-one (also known as Coumarin 7); 7-(diethylamino)-3-(1-methylbenzimidazol-2-yl)benzopyran-2-one (also known as Coumarin 30); etc.; and any combination thereof.]

[0070] Preferably, the fluorophore used as light absorber 108 / 132 absorbs electromagnetic radiation at wavelengths of 302 nm or less, or 700 nm or greater, and emits photoluminescence at wavelengths of 302 nm to 700 nm. However, other excitation and emission wavelengths are also suitable.

[0071] When light absorber 132 is applied to particles 124 / 130, light absorber 132 can be suspended and / or dissolved in a solvent. The solvent should not react with the thermoplastic polymer 102 (e.g., not swell and not dissolve). Examples of solvents include, but are not limited to, water, methanol, ethanol, propanol, acetone, benzene, toluene, hexane, heptane, chloroform, etc., and any miscible combinations thereof.

[0072] Particles 124 / 130 may be exposed to solvent-suspended / dissolved light absorber 132 for a suitable amount of time (e.g., about 1 minute to about 48 hours, or about 1 minute to about 6 hours, or about 1 hour to about 24 hours, or about 18 minutes to about 48 hours). Additionally, exposure may be performed at any suitable temperature (e.g., about -10°C to about 100°C, or about -10°C to about 30°C, or about 10°C to about 50°C, or about 50°C to about 100°C). Examples of exposure techniques include, but are not limited to, immersion, washing (e.g., passing the solvent-suspended / dissolved light absorber 132 over a wet filter cake of particles 124 / 130 and / or passing the solvent-suspended / dissolved light absorber 132 through a column filled with particles 124 / 130), spraying, and any combination thereof.

[0073] Alternatively, the light absorber 132, which consists of particles 124 / 130, can be applied as a powder.

[0074] The OACTP particles disclosed herein may contain a light absorber (or, if more than one is used, a cumulative light absorber) in an amount of about 0.01 wt% to about 30 wt% of the thermoplastic polymer 102 (or about 0.01 wt% to about 1 wt%, or about 0.1 wt% to about 5 wt%, or about 1 wt% to about 10 wt%, or about 5 wt% to about 20 wt%, or about 10 wt% to about 30 wt%).

[0075] OACTP particles may contain one or more light absorbers. The composition and concentration of the light absorbers can be used to identify, track, verify, and / or determine the health status of articles made from OACTP particles. That is, the light absorbers can be used as chemical fingerprints for identifying, tracking, and / or verifying articles. Additionally or alternatively, the light absorbers can be used as chemical indicators of a part of an article as a way to identify defects (e.g., cracks or abrasion) and / or the extent of such defects.

[0076] Emulsion stabilizers used in the methods and compositions of this disclosure may comprise nanoparticles (e.g., oxide nanoparticles, carbon black, polymer nanoparticles, and combinations thereof), surfactants, and any combination thereof.

[0077] Oxide nanoparticles can be metal oxide nanoparticles, non-metal oxide nanoparticles, or mixtures thereof. Examples of oxide nanoparticles include, but are not limited to, silica, titanium dioxide, zirconium oxide, aluminum oxide, iron oxide, copper oxide, tin oxide, boron oxide, cerium oxide, thallium oxide, tungsten oxide, and any combination thereof. Mixed metal oxides and / or non-metal oxides such as aluminosilicates, borosilicates, and aluminoborosilicates are also included in the term metal oxide. Oxide nanoparticles can be hydrophilic or hydrophobic, which may be due to the particles being natural or the result of surface treatment. For example, silica nanoparticles with hydrophobic surface treatments (such as dimethylsilyl, trimethylsilyl, etc.) can be used in the methods and compositions of this disclosure. Additionally, silica with functional surface treatments (such as methacrylate functionalization) can be used in the methods and compositions of this disclosure. Non-functionalized oxide nanoparticles may also be suitable for use.

[0078] Commercially available examples of silica nanoparticles include, but are not limited to, those available from Evonik. Particles (e.g., R812S (with hydrophobic modified surface and 260±30m) 2 (approximately 7 nm average diameter silica nanoparticles with a BET surface area of ​​ / g) RX50 (with hydrophobic modified surface and 35±10m) 2 (approximately 40 nm average diameter silica nanoparticles with a surface area of ​​ / g BET) 380 (with a hydrophilic modified surface and 380±30m) 2 / g BET surface area silica nanoparticles) and any combination thereof.

[0079] Carbon black is another type of nanoparticle that can be present in the compositions and methods disclosed herein as an emulsion stabilizer. Various grades of carbon black are well known to those skilled in the art, and any of these grades can be used herein. Similarly, other nanoparticles capable of absorbing infrared radiation can be used.

[0080] Polymer nanoparticles are another type of nanoparticle that may exist in the form of emulsion stabilizers as disclosed herein. Suitable polymer nanoparticles may comprise one or more thermosetting and / or crosslinked polymers such that they do not melt when processed by melt emulsification according to the disclosure herein. High molecular weight thermoplastic polymers with high melting points or decomposition points may similarly comprise suitable polymer nanoparticle emulsion stabilizers.

[0081] Nanoparticles may have an average diameter (D50 based on volume) of about 1 nm to about 500 nm (or about 10 nm to about 150 nm, or about 25 nm to about 100 nm, or about 100 nm to about 250 nm, or about 250 nm to about 500 nm).

[0082] Nanoparticles can have a size of approximately 10 μm 2 / g to approximately 500m 2 / g (or approximately 10 mg) 2 / g to approximately 150m 2 / g, or approximately 25m 2 / g to approximately 100m 2 / g, or approximately 100m 2 / g to approximately 250m 2 / g, or approximately 250m 2 / g to approximately 500m 2 BET surface area (g)

[0083] The nanoparticles may be included in the mixture 112 at a concentration of about 0.01 wt% to about 10 wt% (or about 0.01 wt% to about 1 wt%, or about 0.1 wt% to about 3 wt%, or about 1 wt% to about 5 wt%, or about 5 wt% to about 10 wt%) based on the weight of the thermoplastic polymer 102.

[0084] Surfactants can be anionic, cationic, nonionic, or amphoteric. Examples of surfactants include, but are not limited to, sodium dodecyl sulfate, sorbitan oleate, poly[dimethylsiloxane-co-[3-(2-(2-hydroxyethoxy)ethoxy)propylmethylsiloxane], sodium docusate (1,4-bis(2-ethylhexyloxy)-1,4-dioxobutane-2-sulfonate), and any combination thereof. Commercially available examples of surfactants include, but are not limited to, those listed below. DB-45 (Sodium dodecyl diphenyl ether disulfonate, available from Pilot Chemicals) 80 (Sorbitol maleate nonionic surfactant) Surfactants (available from Stepan Company), TERGITOL TM TMN-6 (a water-soluble, nonionic surfactant, available from Dow Chemical Company (DOW)) and TRITON TM X-100 (octylphenol ethoxylate, available from Sigma-Aldrich) CA-520 (polyoxyethylene (5) isooctylphenyl ether, available from Sigma-Aldrich), S10 (polyethylene glycol octadecyl ether, available from Sigma-Aldrich) and any combination thereof.

[0085] The surfactant may be included in the mixture 112 at a concentration of about 0.01 wt% to about 10 wt% (or about 0.01 wt% to about 1 wt%, or about 0.5 wt% to about 2 wt%, or about 1 wt% to about 3 wt%, or about 2 wt% to about 5 wt%, or about 5 wt% to about 10 wt%) based on the weight of polyamide 102. Alternatively, the mixture 112 may not contain (or may not contain) a surfactant.

[0086] The weight ratio of nanoparticles to surfactant can be from about 1:10 to about 10:1 (or from about 1:10 to about 1:1, or from about 1:5 to about 5:1, or from about 1:1 to about 10:1).

[0087] As described above, components 102, 104, and 106 can be added in any order and include mixing and / or heating during the process of combining components 102, 104, and 106 in combination 110. For example, the emulsion stabilizer 106 can be dispersed in the carrier fluid 104 before adding the thermoplastic polymer 102, optionally heating the dispersion. In another non-limiting example, the thermoplastic polymer 102 can be heated to produce a polymer melt, and the carrier fluid 104 and the emulsion stabilizer 106 can be added together or in any order to the polymer melt. In another non-limiting example, the thermoplastic polymer 102 and the carrier fluid 104 can be mixed at a temperature greater than the melting point or softening temperature of the thermoplastic polymer 102, at a sufficient shear rate to disperse the thermoplastic polymer melt in the carrier fluid 104. The emulsion stabilizer 106 can then be added to form mixture 112 and maintained under suitable processing conditions for a set period of time.

[0088] Components 110 102, 104, and 106 can be combined in any combination within a mixing apparatus and / or another suitable container for processing 114. As a non-limiting example, the thermoplastic polymer 102 can be heated to a temperature greater than its melting point or softening temperature in the mixing apparatus for processing 114, and the emulsion stabilizer 106 can be dispersed in the carrier fluid 104 in another container. The dispersion can then be added to the melt of the thermoplastic polymer 102 in the mixing apparatus for processing 114.

[0089] The mixing apparatus used for processing 114 to produce melt emulsion 116 should be able to maintain melt emulsion 116 at a temperature greater than the melting point or softening temperature of thermoplastic polymer 102 and apply a sufficient shear rate to disperse the polymer melt in droplets in carrier fluid 104.

[0090] Examples of mixing apparatus for processing 114 to produce melt emulsion 116 include, but are not limited to, extruders (e.g., continuous extruders, batch extruders, etc.), stirred reactors, mixers, reactors with in-line homogenizer systems, and apparatus derived therefrom.

[0091] Processing 114 and forming a melt emulsion 116 under suitable processing conditions (e.g., temperature, shear rate, etc.) within a set time period.

[0092] The processing temperature 114 and the temperature at which the melt emulsion 116 is formed should be greater than the melting point or softening temperature of the thermoplastic polymer 102 and less than the decomposition temperature of any component 102, 104, and 106 in the mixture 112. For example, the processing temperature 114 and the temperature at which the melt emulsion 116 is formed may be about 1°C to about 50°C (or about 1°C to about 25°C, or about 5°C to about 30°C, or about 20°C to about 50°C) greater than the melting point or softening temperature of the thermoplastic polymer 102, provided that the processing temperature 114 and the temperature at which the melt emulsion 116 is formed are less than the decomposition temperature of any component 102, 104, and 106 in the mixture 112.

[0093] The shear rate of processing 114 and forming the melt emulsion 116 should be high enough to disperse the polymer melt in droplets in the carrier fluid 104. The droplets should comprise droplets having a diameter of about 1000 μm or less (or about 1 μm to about 1000 μm, or about 1 μm to about 50 μm, or about 10 μm to about 100 μm, or about 10 μm to about 250 μm, or about 50 μm to about 500 μm, or about 250 μm to about 750 μm, or about 500 μm to about 1000 μm).

[0094] The time for maintaining the temperature and shear rate of processing 114 and forming the molten emulsion 116 can be from 10 seconds to 18 hours or longer (or 10 seconds to 30 minutes, or 5 minutes to 1 hour, or 15 minutes to 2 hours, or 1 hour to 6 hours, or 3 hours to 18 hours). Without being theoretically limited, it is believed that a steady state of droplet size will be reached, at which point processing 114 can be stopped. Among other things, this time may also depend on the temperature, shear rate, composition of the thermoplastic polymer 102, composition of the carrier fluid 104, and composition of the emulsion stabilizer 106.

[0095] The molten emulsion 116 can then be cooled 118. Cooling 118 can range from slow (e.g., allowing the molten emulsion to cool under ambient conditions) to fast (e.g., quenching). For example, the cooling rate can be in the range of almost instantaneous from about 10°C / hour to about 100°C / second to quenching (e.g. in dry ice) (or about 10°C / hour to about 60°C / hour, or about 0.5°C / min to about 20°C / min, or about 1°C / min to about 5°C / min, or about 10°C / min to about 60°C / min, or about 0.5°C / second to about 10°C / second, or about 10°C / second to about 100°C / second).

[0096] During cooling, little or no shear may be applied to the molten emulsion 116. In some cases, the shear applied during heating may also be applied during cooling.

[0097] The cooled mixture 120 obtained from the cooled melt emulsion 116 comprises solidified thermoplastic polymer particles 124 (or simply thermoplastic polymer particles) and other components 126 (e.g., carrier fluid 104, excess emulsion stabilizer 106, etc.). The thermoplastic polymer particles may be dispersed in the carrier fluid or settled in the carrier fluid.

[0098] The cooled mixture 120 can then be processed to separate the thermoplastic polymer particles 124 (or simply thermoplastic polymer particles 124) from the other components 126. Suitable processes include, but are not limited to, washing, filtration, centrifugation, decantation, and any combination thereof.

[0099] The solvent used for washing the thermoplastic polymer particles 124 should generally be (a) miscible with the carrier fluid 104 and (b) non-reactive with the thermoplastic polymer 102 (e.g., non-swelling and non-dissolving). Among other things, the choice of solvent will also depend on the composition of the carrier fluid and the composition of the thermoplastic polymer 102.

[0100] Examples of solvents include, but are not limited to, hydrocarbon solvents (e.g., pentane, hexane, heptane, octane, cyclohexane, cyclopentane, decane, dodecane, tridecane, and tetradecane), aromatic hydrocarbon solvents (e.g., benzene, toluene, xylene, 2-methylnaphthalene, and cresol), ether solvents (e.g., diethyl ether, tetrahydrofuran, diisopropyl ether, and dioxane), ketone solvents (e.g., acetone and methyl ethyl ketone), alcohol solvents (e.g., methanol, ethanol, isopropanol, and n-propanol), ester solvents (e.g., ethyl acetate, methyl acetate, butyl acetate, butyl propionate, and butyl butyrate), halogenated solvents (e.g., chloroform, bromoform, 1,2-dichloromethane, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, and hexafluoroisopropanol), water, and any combination thereof.

[0101] The solvent can be removed from the thermoplastic polymer particles 124 by drying using suitable methods (such as air drying, heat drying, vacuum drying, freeze drying, or a combination thereof). Heating can preferably be performed at a temperature below the glass transition point of the thermoplastic polymer (e.g., about 50°C to about 150°C).

[0102] Advantageously, the carrier fluid and washing solvent of the systems and methods described herein (e.g., method 100) can be recycled and reused. Those skilled in the art will recognize any necessary cleaning of the used carrier fluid and solvent required during the recycling process.

[0103] After separation from other components 126 and / or after application of light absorber 132 134, the thermoplastic polymer particles 124 may optionally be further purified 128. As shown, purification 128 occurs prior to application of light absorber 132 134 and produces purified thermoplastic polymer particles 130. For example, to narrow the particle size distribution (or reduce the diameter span), the thermoplastic polymer particles 124 (before and / or after application of light absorber 132 134) may be passed through a sieve having a pore size of about 10 μm to about 250 μm (or about 10 μm to about 100 μm, or about 50 μm to about 200 μm, or about 150 μm to about 250 μm).

[0104] In another example purification technique, the thermoplastic polymer particles 124 may be washed with water (before and / or after the application of light absorber 132) to remove surfactants while retaining substantially all nanoparticles associated with the surface of the thermoplastic polymer particles 124. In yet another example purification technique, the thermoplastic polymer particles 124 (before and / or after the application of light absorber 132) may be blended with additives to achieve a desired final product. For clarity, since such additives are blended with the thermoplastic particles 124 or other particles obtained by the methods described herein after particle coagulation, such additives are referred to herein as “external additives.” Examples of external additives include flow aids, other polymer particles, fillers, etc., and any combination thereof.

[0105] In some cases, the surfactant used to prepare the thermoplastic polymer particles 124 may be undesirable in downstream applications. Therefore, another example purification technique may include at least substantially removing the surfactant from the thermoplastic polymer particles 124 (before and / or after the application of the light absorber 132 134) (e.g., by washing and / or pyrolysis).

[0106] The thermoplastic polymer particles 124 and / or purified thermoplastic polymer particles 130 and / or OACTP particles 136 (referred to as particles 124 / 130 / 136) can be characterized by composition, physical structure, etc.

[0107] As described above, the emulsion stabilizer is located at the interface between the polymer melt and the carrier fluid. Therefore, when the mixture is cooled, the emulsion stabilizer remains at or near the interface. Thus, when using an emulsion stabilizer, the structure of particles 124 / 130 / 136 typically comprises (a) an emulsion stabilizer dispersed on the outer surface of particles 124 / 130 / 136 and / or (b) an emulsion stabilizer embedded in the exterior (e.g., 1% by volume) of particles 124 / 130 / 136.

[0108] Furthermore, in cases where voids are formed within the polymer melt droplets, the emulsion stabilizer 106 should generally be located at the interface between the voids and the thermoplastic polymer (and / or embedded in the interface). The voids typically do not contain the thermoplastic polymer. Instead, the voids may contain, for example, a fluid carrier, air, or be empty. Particles 124 / 130 / 136 may contain about 5% by weight or less (or about 0.001% by weight to about 5% by weight, or about 0.001% by weight to about 0.1% by weight, or about 0.01% by weight to about 0.5% by weight, or about 0.1% by weight to about 2% by weight, or about 1% by weight to about 5% by weight) of a fluid carrier.

[0109] Thermoplastic polymer 102 may be present in particles 124 / 130 / 136 in an amount of about 90% to about 99.5% by weight (or about 90% to about 95% by weight, or about 92% to about 97% by weight, or about 95% to about 99.5% by weight).

[0110] Emulsion stabilizer 106 may be present in particles 124 / 130 / 136 in about 10% by weight or less (or about 0.01% by weight to about 10% by weight, or about 0.01% by weight to about 1% by weight, or about 0.5% by weight to about 5% by weight, or about 3% by weight to about 7% by weight, or about 5% by weight to about 10% by weight). When purified to at least substantially remove a surfactant or another emulsion stabilizer, emulsion stabilizer 106 may be present in particles 130 / 136 in less than 0.01% by weight (or 0% by weight to about 0.01% by weight, or 0% by weight to 0.001% by weight).

[0111] When forming thermoplastic microparticles according to the present disclosure using a particulate emulsion stabilizer, at least a portion of the particulate emulsion stabilizer, such as silica nanoparticles, can be disposed as a coating on the outer surface of the thermoplastic microparticles. At least a portion of a surfactant (if used) may also associate with the outer surface. The coating can be disposed substantially uniformly on the outer surface. As used herein with respect to coating, the term "substantially uniform" refers to a uniform coating thickness across the surface area covered by the coating composition (e.g., nanoparticles and / or surfactant), particularly across the entire outer surface. The emulsion stabilizer 106 can form a coating covering at least 5% (or about 5% to about 100%, or about 5% to about 25%, or about 20% to about 50%, or about 40% to about 70%, or about 50% to about 80%, or about 60% to about 90%, or about 70% to about 100%) of the surface area of ​​the particles 124 / 130 / 136. When purified to at least substantially remove the surfactant or another emulsion stabilizer, the emulsion stabilizer 106 may be present in less than 25% (or 0% to about 25%, or about 0.1% to about 5%, or about 0.1% to about 1%, or about 1% to about 5%, or about 1% to about 10%, or about 5% to about 15%, or about 10% to about 25%) of the surface area of ​​the particles 130 / 136. The coverage of the emulsion stabilizer 106 on the outer surface of the particles 124 / 130 / 136 can be determined using image analysis of scanning electron microscopy (SEM micrographs). The emulsion stabilizer 106 may form a coating covering at least 5% (or about 5% to about 100%, or about 5% to about 25%, or about 20% to about 50%, or about 40% to about 70%, or about 50% to about 80%, or about 60% to about 90%, or about 70% to about 100%) of the surface area of ​​particles 124 / 130 / 136. When purified to at least substantially remove a surfactant or another emulsion stabilizer, the emulsion stabilizer 106 may be present in particles 130 / 136 in less than 25% (or 0% to about 25%, or about 0.1% to about 5%, or about 0.1% to about 1%, or about 1% to about 5%, or about 1% to about 10%, or about 5% to about 15%, or about 10% to about 25%) of the surface area of ​​particles 130 / 136. Image analysis using SEM micrographs can be used to determine the coverage of emulsion stabilizer 106 on the outer surface of particles 124 / 130 / 136.

[0112] The particles 124 / 130 / 136 may have a D10 of about 0.1 μm to about 125 μm (or about 0.1 μm to about 5 μm, about 1 μm to about 10 μm, about 5 μm to about 30 μm, or about 1 μm to about 25 μm, or about 25 μm to about 75 μm, or about 50 μm to about 85 μm, or about 75 μm to about 125 μm), a D50 of about 0.5 μm to about 200 μm (or about 0.5 μm to about 10 μm, or about 5 μm to about 50 μm, or about 30 μm to about 100 μm, or about 30 μm to about 70 μm, or about 25 μm to about 50 μm, or about 50 μm to about 100 μm, or about 75 μm to about 150 μm, or about 100 μm to about 200 μm), and a D90 of about 3 μm to about 300 μm (or about 3 μm to about 15 μm, or about 10 μm to about 50 μm, or about 25 μm to about 75 μm, or about 70 μm to about 200 μm, or about 60 μm to about 150 μm, or about 150 μm to about 300 μm), where D10 < D50 < D90. The particles 124 / 130 / 136 may also have a diameter span of about 0.2 to about 10 (or about 0.2 to about 0.5, or about 0.4 to about 0.8, or about 0.5 to about 1.0, or about 1 to about 3, or about 2 to about 5, or about 5 to about 10). Without limitation, a diameter span value of 1.0 or greater is considered wide, and a diameter span value of 0.75 or less is considered narrow.

[0113] In a first non - limiting example, the particles 124 / 130 / 136 may have a D10 of about 0.1 μm to about 10 μm, a D50 of about 0.5 μm to about 25 μm, and a D90 of about 3 μm to about 50 μm, where D 10 < D50 < D90. The particles 124 / 130 / 136 may have a diameter span of about 0.2 to about 2.

[0114] In a second non - limiting example, the particles 124 / 130 / 136 may have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and a D90 of about 70 μm to about 120 μm, where D10 < D50 < D90. The particles 124 / 130 / 136 may have a diameter span of about 1.0 to about 2.5.

[0115] In a third non - limiting example, the particles 124 / 130 / 136 may have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about 110 μm, and a D90 of about 110 μm to about 175 μm, where D10 < D50 < D90. The particles 124 / 130 / 136 may have a diameter span of about 0.6 to about 1.5.

[0116] In a fourth non-limiting example, the particles 124 / 130 / 136 may have a D10 of from about 75 μm to about 125 μm, a D50 of from about 100 μm to about 200 μm, and a D90 of from about 125 μm to about 300 μm, where D10 < D50 < D90. The particles 124 / 130 / 136 may have a diameter span of from about 0.2 to about 1.2.

[0117] In a fifth non-limiting example, the particles 124 / 130 / 136 may have a D10 of from about 1 μm to about 50 μm (or from about 5 μm to about 30 μm, or from about 1 μm to about 25 μm, or from about 25 μm to about 50 μm), a D50 of from about 25 μm to about 100 μm (or from about 30 μm to about 100 μm, or from about 30 μm to about 70 μm, or from about 25 μm to about 50 μm, or from about 50 μm to about 100 μm), and a D90 of from about 60 μm to about 300 μm (or from about 70 μm to about 200 μm, or from about 60 μm to about 150 μm, or from about 150 μm to about 300 μm), where D10 < D50 < D90. The particles 124 / 130 / 136 may also have a diameter span of from about 0.4 to about 3 (or from about 0.6 to about 2, or from about 0.4 to about 1.5, or from about 1 to about 3).

[0118] The particles 124 / 130 / 136 may have a roundness of about 0.9 or greater (or from about 0.90 to about 1.0, or from about 0.93 to about 0.99, or from about 0.95 to about 0.99, or from about 0.97 to about 0.99, or from about 0.98 to 1.0).

[0119] The particles 124 / 130 / 136 may have an angle of repose of from about 25° to about 45° (or from about 25° to about 35°, or from about 30° to about 40°, or from about 35° to about 45°).

[0120] The particles 124 / 130 / 136 may have a Hausner ratio of from about 1.0 to about 1.5 (or from about 1.0 to about 1.2, or from about 1.1 to about 1.3, or from about 1.2 to about 1.35, or from about 1.3 to about 1.5).

[0121] The particles 124 / 130 / 136 may have a density of from about 0.3 g / cm 3 to about 0.8 g / cm 3 (or from about 0.3 g / cm 3 to about 0.6 g / cm 3 , or from about 0.4 g / cm 3 to about 0.7 g / cm 3 , or from about 0.5 g / cm 3 to about 0.6 g / cm 3 , or from about 0.5 g / cm 3Approximately 0.8 g / cm³ 3 The packing density of ).

[0122] Depending on the temperature and shear rate of processing 114, and the composition and relative concentration of components 102, 104, and 106, different shapes of the structures constituting particles 124 / 130 / 136 have been observed. Typically, particles 124 / 130 / 136 comprise substantially spherical particles (having a roundness of about 0.97 or greater). However, other structures, including discs and elongated structures, have been observed in particles 124 / 130 / 136. Therefore, particles 124 / 130 / 136 may comprise one or more of the following: (a) substantially spherical particles having a roundness of 0.97 or greater, (b) disc structures having an aspect ratio of about 2 to about 10, and (c) elongated structures having an aspect ratio of 10 or greater. Each of structures (a), (b), and (c) has an emulsion stabilizer dispersed on the outer surface of structures (a), (b), and (c) and / or embedded in the exterior of structures (a), (b), and (c). At least some of the structures (a), (b), and (c) can aggregate. For example, the elongated structure (c) can be laid on the surface of the substantially spherical particles of (a).

[0123] Particles 124 / 130 / 136 may have a sintering window within 10°C, preferably within 5°C, of ​​the thermoplastic polymer sintering window.

[0124] Applications of OACTP-Polyamide

[0125] The OACTP-polyamide described herein can be used to produce a variety of articles (or products). The OACTP-polyamide described herein can be used alone or in combination with other thermoplastic polymers (e.g., light-absorbing polyamides and / or other thermoplastic polymers). Examples of thermoplastic polymers that can be used with one or more OACTP-polyamides disclosed herein include, but are not limited to, polyamides, polyurethanes, polyethylene, polypropylene, polyacetals, polycarbonates, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene terephthalate (PTT), hexane terephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyesters (e.g., polylactic acid), polyethers, polyethersulfones, polyetheretherketones, polyacrylates, polymethacrylates, polyimides, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide, vinyl polymers, polyaryl ethers, polyaryl sulfides, polysulfones, polyetherketones, polyamide-imides, polyetherimides, polyether esters, copolymers comprising polyether blocks and polyamide blocks (PEBA or polyether block amides), etc. Grafted or ungrafted thermoplastic polyolefins, functionalized or unfunctionalized ethylene / vinyl monomer polymers, functionalized or unfunctionalized ethylene / (meth)acrylate alkyl esters, functionalized or unfunctionalized (meth)acrylate polymers, functionalized or unfunctionalized ethylene / vinyl monomer / (meth)acrylate alkyl ester terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / (meth)acrylate alkyl ester / carbonyl terpolymers, methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene / vinyl acetate), polybutadiene, polyisoprene, styrene-based block copolymers, polyacrylonitrile, silicone, and any combination thereof. Copolymers containing one or more of the foregoing substances may also be used in the methods and systems described herein.

[0126] If desired, compatibilizers may be used when combining the OACTP-polyamide described herein with other thermoplastic polymers. Compatibilizers can improve the blending efficiency and / or effectiveness of the polymer. Examples of polymer compatibilizers include, but are not limited to, PROPOLDER. TM MPP2020 20 (Polypropylene, available from Polygroup Inc.), PROPOLDER TM MPP2040 40 (Polypropylene, available from Polygroup Inc.) and NOVACOM TMHFS2100 (maleic anhydride-functionalized high-density polyethylene polymer, available from Polygroup Inc.) and KEN-REACT TM CAPS TM L TM 12 / L (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM CAPOW TM L TM 12 / H (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM LICA TM 12 (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM CAPS TM KPR TM 12 / LV (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM CAPOW TM KPR TM 12 / H (organometallic coupling agent, available from Kenrich Petrochemicals) and KEN-REACT TM Titanates and zirconates (organometallic coupling agents, available from Kenrich Petrochemicals), VISTAMAXX TM (Ethylene-propylene copolymer, available from ExxonMobil), SANTOPRENE TM (Ethylene propylene diene monomer (EPDM) and polypropylene thermoplastic vulcanizates are available from ExxonMobil and Vistalon.) TM (EPDM rubber, available from ExxonMobil) and EXACT TM (Plastic material, available from ExxonMobil) TM (Polymer resin, available from ExxonMobil) FUSABOND TM M603 (random ethylene copolymer, available from Dow Chemical Company (DOW)) and FUSABOND TME226 (anhydride-modified polyethylene, available from Dow Chemical Company (DOW)), BYNEL TM 41E710 (co-extrudeable adhesive resin, available from Dow Chemical Company (DOW)), SURLYN TM 1650 (ionomer resin, available from Dow Chemical Company (DOW)), FUSABOND TM P353 (a chemically modified polypropylene copolymer, available from Dow Chemical Company (DOW)) and ELVALOY TM PTW (ethylene terpolymer, available from Dow Chemical Company (DOW)) and ELVALOY TM 3427AC (a copolymer of ethylene and butyl acrylate, available from Dow Chemical Company (DOW)) and LOTADER TM AX8840 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 3210 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 3410 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 3430 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 4700 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM AX8900 (a terpolymer based on ethylene-acrylate, available from Arkema), LOTADER TM 4720 (a terpolymer based on ethylene-acrylate, available from Arkema), BAXXODUR TM EC 301 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC311 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 303 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 280 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 201 (an amine for epoxy resins, available from BASF), BAXXODUR TMEC 130 (an amine for epoxy resins, available from BASF), BAXXODUR TM EC 110 (an amine for epoxy resins, available from BASF), styrene, polypropylene, polyamide, polycarbonate, EASTMAN TM G-3003 (a maleic anhydride-grafted polypropylene, available from Eastman), RETAIN TM (Polymer modifier, available from Dow Chemical Company (DOW)), AMPLIFY TY TM (Maleic anhydride grafted polymer, available from Dow Chemical Company (DOW) and INTUNE) TM (olefin block copolymers, available from Dow Chemical Company (DOW)) and any combination thereof.

[0127] Methods for preparing articles include, but are not limited to, melt extrusion, injection molding, compression molding, melt spinning, melt emulsification, spray drying (e.g., to form granules), cryogenic milling (or cryogenic grinding), freeze-drying of polymer dispersions, polymer dispersion precipitation, and any mixing thereof.

[0128] Examples of articles that can be produced by such methods, in which OACTP-polyamide can be all or part of the article, include, but are not limited to, granules, films, packaging, toys, household goods, automotive parts, aerospace / aircraft related parts, containers (e.g., for food, beverages, cosmetics, personal care compositions, pharmaceuticals, etc.), shoe soles, furniture parts, decorative home furnishings, plastic gears, screws, nuts, bolts, cable ties, jewelry, artwork, sculptures, medical supplies, prostheses, orthopedic implants, production of artifacts for assisting learning in education, 3D anatomical models for assisting surgery, robots, biomedical devices (orthotics), household appliances, dental devices, electronic devices, sporting goods, etc. Additionally, granules can be used in applications including, but not limited to, paints, powder coatings, inkjet materials, electrophotographic toners, 3D printing, etc.

[0129] Furthermore, the OACTP-polyamide described herein may have a specific chemical fingerprint for identifying, tracking, verifying, and / or determining the health status of articles. Additionally, the location of the OACTP-polyamide within the article constitutes another layer for fingerprinting the article, used for identifying, tracking, verifying, and / or determining its health status.

[0130] Methods for identifying, tracking, verifying, and / or determining the health status of articles may include (a) exposing an article containing OACTP-polyamide to electromagnetic radiation (e.g., for fluorophores preferably at wavelengths of 302 nm or less or 700 nm or greater); (b) sensing one or more spectra associated with the absorbed and / or re-emitted electromagnetic radiation (e.g., photoluminescence emitted, preferably between 302 nm and 700 nm, for fluorophores); and (c) comparing the spectrum of a light absorber used in the article or a portion thereof with a known spectrum. Optionally, the location of a spectral region on the article may be compared with a known location where the spectral region should be located. This comparison may be used to identify and / or verify the article. For tracking purposes, the comparison and / or recording of the detected spectra and / or spectral regions, along with the physical location of the article, may be made in a database. Furthermore, the health status of worn and / or broken articles may be detected. For example, the core portion of an article may include a light absorber, and an outer portion may cover the core portion and not include the light absorber (or include a different light absorber). Then, when comparing spectra, the appearance of spectral characteristics of the light absorber in the core can indicate that the article is at or near the end of its lifespan.

[0131] As a non-limiting example, the 3D printing process of this disclosure may include: depositing particles comprising one or more of the OACTP-polyamides of this disclosure (and optionally one or more other thermoplastic polymers and / or one or more compatibilizers) in a specified shape onto a surface, and once deposited, heating at least a portion of the particles to promote their consolidation and form a consolidated body (or article) such that the consolidated body has a void percentage of about 1% or less after consolidation. For example, the heating and consolidation of the thermoplastic polymer particles may be performed in a 3D printing apparatus employing a laser, such that the heating and consolidation are carried out by selective laser sintering.

[0132] As a non-limiting example, the 3D printing process of this disclosure may include: extruding a filament comprising one or more of the OACTP-polyamides of this disclosure (and optionally one or more other thermoplastic polymers and / or one or more compatibilizers) and passing it through an orifice, wherein the filament becomes a polymer melt during extrusion; depositing the polymer melt as a first layer on a platform; cooling the layer; depositing an additional layer of polymer melt on the first layer; cooling the additional layer; and repeating the deposition and cooling of at least one additional layer to produce a 3D shape.

[0133] Another non-limiting example is a method comprising: extruding a polymer melt containing one or more OACTP-polyamides of this disclosure (and optionally one or more other thermoplastic polymers and / or one or more compatibilizers) and passing it through an orifice to produce films, fibers (or filaments), granules, pellets, etc.

[0134] Example Implementation Plan

[0135] A method according to a first non-limiting example embodiment includes: mixing a mixture comprising the thermoplastic polymer, a carrier fluid immiscible with the thermoplastic polymer, and optionally an emulsion stabilizer at a temperature above the melting or softening temperature of the thermoplastic polymer and at a shear rate sufficiently high to disperse the thermoplastic polymer in a carrier fluid; cooling the mixture to below the melting or softening temperature of the thermoplastic polymer to form solidified particles comprising the thermoplastic polymer; separating the solidified particles from the carrier fluid; and exposing the solidified particles to a light absorber to produce thermoplastic polymer particles containing the light absorber (OACTP particles). Furthermore, the light absorber may be a first light absorber, and the mixture may also include a second light absorber that is the same as or different from the first light absorber.

[0136] A second non-limiting example embodiment of the method includes: mixing a mixture comprising the thermoplastic polymer, a carrier fluid immiscible with the thermoplastic polymer, a light absorber, and optionally an emulsion stabilizer at a temperature greater than the melting or softening temperature of the thermoplastic polymer and at a sufficiently high shear rate to disperse the thermoplastic polymer in a carrier fluid; cooling the mixture to below the melting or softening temperature of the thermoplastic polymer to form solidified light absorber-containing thermoplastic polymer particles (OACTP particles), the solidified light absorber-containing thermoplastic polymer particles comprising the thermoplastic polymer and the light absorber; and separating the solidified OACTP particles from the carrier fluid.

[0137] The first and second example embodiments may optionally include one or more of the following: Element 1: wherein, based on the weight of the thermoplastic polymer in the OACTP particles, the OACTP particles contain 0.01% to 30% by weight of a light absorber; Element 2: wherein the light absorber is selected from: rhodamine, fluorescein, coumarin, naphthalenediimide, benzoxanthracene, acridine, cyanine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polymethystylene, triarylmethane, anthraquinone, pyrazolone, quinoline ketone, carbonyl dye, diazo dye, phenanthrene, pyrrolopyrroledione (DPP), dioxazine dye, phthalocyanine, indigoanthraquinone, benzoxanthone, violet anthrone, azo dye, phthalocyanine dye, quinacridone dye, anthraquinone dye. Element 1: Indigo dye, thio-indigo dye, pyrene dye, dinaphthalene-based dye, isoindole dye, aromatic amino acids, flavin, pyridoxine derivatives, chlorophyll derivatives, and any combination thereof; Element 2: Wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises a surfactant and / or nanoparticles; Element 3: Wherein Element 3 and wherein the emulsion stabilizer associates with the outer surface of the OACTP particles; Element 4: Wherein Element 3 and wherein the emulsion stabilizer is embedded in the outer surface; Element 5: Wherein Element 3 and wherein the emulsion stabilizer is embedded in the outer surface; Element 6: Wherein the thermoplastic polymer is selected from: polyamide, polyurethane, polyethylene, polypropylene, polyacetal, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate. Poly(ethylene terephthalate) (PEN), polypropylene terephthalate (PTT), polyhexane terephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyester (e.g., polylactic acid), polyether, polyethersulfone, polyetheretherketone, polyacrylate, polymethacrylate, polyimide, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide, vinyl polymers, polyaryl ethers, polyaryl sulfides, polysulfone, polyetherketone, polyamide-imide, polyetherimide, polyether ester, copolymers containing polyether blocks and polyamide blocks (PEBA or polyether block amide), grafted or ungrafted thermoplastic polyolefins, functionalized or unfunctionalized ethylene / vinyl monomer polymers, functionalized or unfunctionalized ethylene / (meth)acrylate alkyl groups Acrylic esters, functionalized or unfunctionalized (meth)acrylic acid polymers, functionalized or unfunctionalized ethylene / vinyl monomer / (meth)acrylic acid alkyl ester terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / (meth)acrylic acid alkyl ester / carbonyl terpolymers, methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene / vinyl acetate), polybutadiene, polyisoprene, styrene-based block copolymers, polyacrylonitrile, organosilicon, and any combination thereof;Element 7: At least some of the OACTP particles have voids, the voids containing an emulsion stabilizer at the void / thermoplastic polymer interface; Element 8: Element 7, wherein the emulsion stabilizer is included in the mixture, and wherein the emulsion stabilizer comprises nanoparticles embedded in the void / polymer interface; Element 9: Element 7, wherein the voids contain a fluid carrier; Element 10: The OACTP particles further include elongated structures on the surface of the OACTP particles, wherein the elongated structures comprise a thermoplastic polymer and the emulsion stabilizer (when included) associates with the outer surface of the elongated structures; Element 11: The emulsion stabilizer is included in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering less than 5% of the surface of the OACTP particles; Element 12: The emulsion stabilizer is included in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 5% of the surface of the OACTP particles; Element 13: The emulsion stabilizer is included in the mixture. The mixture contains an emulsion stabilizer and forms a coating covering at least 25% of the surface of the OACTP particles; Element 14: the emulsion stabilizer is contained in the mixture and forms a coating covering at least 50% of the surface of the OACTP particles; Element 15: the thermoplastic polymer is present in the mixture at a weight percentage of 5% to 60%; Element 16: the emulsion stabilizer is contained in the mixture and is present in the mixture at a weight percentage of 0.05% to 5%; Element 17: the emulsion stabilizer is contained in the mixture and comprises nanoparticles with an average diameter of 1 nm to 500 nm; Element 18: the carrier fluid is selected from: silicone oil, fluorinated silicone oil, perfluorinated silicone oil, polyethylene glycol, alkyl-terminated polyethylene glycol (e.g., C1-C4 terminal alkyl, such as tetraethylene glycol dimethyl ether (TDG)), alkanes, liquid petrolatum, mink oil (Vinson). Oils, turtle oil, soybean oil, squalene, sweet almond oil, calophyllum oil, palm oil, parleam oil, grapeseed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, almond oil, castor oil, avocado oil, jojoba oil, olive oil, cereal germ oil, esters of lanolic acid, esters of oleic acid, esters of lauric acid, esters of stearic acid, fatty acid esters, higher fatty acids, fatty alcohols, polysiloxanes modified with fatty acids, polysiloxanes modified with fatty alcohols, polysiloxanes modified with polyoxyethylene, and any combination thereof;Element 19: Element 18, wherein the silicone oil is selected from: polydimethylsiloxane, methylphenyl polysiloxane, alkyl-modified polydimethylsiloxane, alkyl-modified methylphenyl polysiloxane, amino-modified polydimethylsiloxane, amino-modified methylphenyl polysiloxane, fluorinated polydimethylsiloxane, fluorinated methylphenyl polysiloxane, polyether-modified polydimethylsiloxane, polyether-modified methylphenyl polysiloxane, and any combination thereof; Element 20: wherein the carrier fluid has a viscosity of 1,000 cSt to 150,000 cSt at 25°C; Element 21: wherein the density of the carrier fluid is 0.6 g / c; 3 m to 1.5 g / cm 3; Element 22: wherein the mixing is carried out in an extruder; Element 23: wherein the mixing is carried out in a stirred reactor; Element 24: wherein the emulsion stabilizer contains a surfactant; Element 25: wherein the OACTP particles have a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm, and a D90 of about 3 μm to about 300 μm, where D10 < D50 < D90; Element 26: wherein the OACTP particles have a diameter span of about 0.2 to about 10; Element 27: wherein the OACTP particles have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and a D90 of about 70 μm to about 120 μm, where D10 < D50 < D90; Element 28: wherein the OACTP particles have a diameter span of about 1.0 to about 2.5; Element 29: wherein the OACTP particles have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about 110 μm, and a D90 of about 110 μm to about 175 μm, where D10 < D50 < D90; Element 30: wherein the OACTP particles have a diameter span of about 0.6 to about 1.5; Element 31: wherein the OACTP particles have a D10 of about 75 μm to about 125 μm, a D50 of about 100 μm to about 200 μm, and a D90 of about 125 μm to about 300 μm, where D10 < D50 < D90; Element 32: wherein the OACTP particles have a diameter span of about 0.2 to about 1.2; Element 33: wherein the OACTP particles have a roundness of about 0.90 to about 1.0; Element 34: wherein the OACTP particles have a Hausner ratio of about 1.0 to about 1.5; Element 35: wherein the emulsion stabilizer is contained in the mixture and contains nanoparticles, and wherein the nanoparticles contain oxide nanoparticles; Element 36: wherein the emulsion stabilizer is contained in the mixture and contains nanoparticles, and wherein the nanoparticles contain carbon black; and Element 37: wherein the emulsion stabilizer is contained in the mixture and contains nanoparticles, and wherein the nanoparticles contain polymer nanoparticles. Examples of combinations include, but are not limited to, the combination of Element 1 with one or more of Elements 2 to 37; the combination of two or more of Elements 2 to 4, and optionally a further combination with one or more of Elements 5 to 37; the combination of two or more of Elements 7 to 10; the combination of two or more of Elements 18 to 21; the combination of Element 25 and Element 26; the combination of Element 27 and Element 28; the combination of Element 29 and Element 30; the combination of Element 31 and Element 32; the combination of one or more of Elements 25 to 32 with one or more of Elements 34 and / or 35; the combination of two or more of Elements 35 to 37; the combination of two or more of Elements 17, 24, 35, 36, and 37.

[0138] The composition of the third non-limiting example embodiment comprises: light-absorbing thermoplastic polymer particles (OACTP particles) containing a thermoplastic polymer and a light absorber non-covalently bonded to the thermoplastic polymer, wherein the particles have a roundness of about 0.90 to about 1.0. The third example embodiment may optionally include one or more of the following: element 1; element 2; element 6; element 25; element 26; element 27; element 28; element 29; element 30; element 31; element 32; element 33; element 34; element 35; element 38: wherein the OACTP particles further comprise an emulsion stabilizer associated with the outer surface of the OACTP particles; element 39: wherein the OACTP particles further comprise an emulsion stabilizer, and wherein at least some of the OACTP particles have voids that contain the emulsion stabilizer at the void / polymer interface; element 40: element 39 and wherein the emulsion stabilizer comprises nanoparticles and the nanoparticles are embedded in the void / polymer interface; element 41: element 39 and wherein the voids comprise a fluid carrier; and element 42: wherein the OACTP particles further comprise elongated structures on the surface of the OACTP particles, wherein the elongated structures comprise a thermoplastic polymer and the emulsion stabilizer is associated with the outer surface of the elongated structures.

[0139] Terms and Conditions

[0140] Clause 1. A method comprising: mixing a mixture comprising the thermoplastic polymer, the carrier fluid immiscible with the thermoplastic polymer, and optionally an emulsion stabilizer at a temperature greater than the melting point or softening temperature of the thermoplastic polymer and at a shear rate sufficiently high to disperse the thermoplastic polymer in a carrier fluid; cooling the mixture to below the melting point or softening temperature of the thermoplastic polymer to form solidified particles comprising the thermoplastic polymer; separating the solidified particles from the carrier fluid; and exposing the solidified particles to a light absorber to produce thermoplastic polymer particles containing the light absorber (OACTP particles).

[0141] Clause 2. The method according to Clause 1, wherein the light absorber is a first light absorber, and wherein the mixture further comprises a second light absorber.

[0142] Clause 3. The method according to Clause 2, wherein the first light absorber and the second light absorber are different.

[0143] Clause 4. The method according to Clause 1, wherein the OACTP particles contain 0.01% to 30% by weight of the light absorber based on the weight of the thermoplastic polymer in the OACTP particles.

[0144] Clause 5. The light absorber described in Clause 1 is selected from: rhodamine, fluorescein, coumarin, naphthalenedicarboximide, benzoxanthracene, acridine, cyanine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polyacetylenes, triarylmethane, anthraquinone, pyrazolone, quinophthalone, carbonyl dyes, diazo dyes, phenanthrone, pyrrolopyrroledione (DPP), dioxazine dyes, phthalocyanine, indigoanthraquinone, benzoanthraquinone, violetanthraquinone, azo dyes, phthalocyanine dyes, quinacridone dyes, anthraquinone dyes, indigo dyes, thio-indigo dyes, pyrenone dyes, dinaphthalene-phenylene dyes, isoindole dyes, aromatic amino acids, flavins, pyridoxine derivatives, chlorophyll derivatives, and any combination thereof.

[0145] Clause 6. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises a surfactant and / or nanoparticles.

[0146] Clause 7. The method according to Clause 6, wherein the emulsion stabilizer associates with the outer surface of the OACTP particles.

[0147] Clause 8. The method according to Clause 7, wherein the emulsion stabilizer is embedded in the outer surface.

[0148] Clause 9. The thermoplastic polymer described according to Clause 1 is selected from: polyamide, polyurethane, polyethylene, polypropylene, polyacetal, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene terephthalate (PTT), polyhexane terephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyester (e.g., polylactic acid), polyether, polyethersulfone, polyetheretherketone, polyacrylate, polymethacrylate, polyimide, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide, vinyl polymers, polyaryl ethers, polyaryl sulfides, polysulfone, polyetherketone, polyamide-imide, polyetherimide, polyether ester, copolymers comprising polyether blocks and polyamide blocks (PEBA or polyether block amide), grafted or ungrafted thermoplastics. Polyolefins, functionalized or unfunctionalized ethylene / vinyl monomer polymers, functionalized or unfunctionalized ethylene / (meth)acrylate alkyl esters, functionalized or unfunctionalized (meth)acrylate polymers, functionalized or unfunctionalized ethylene / vinyl monomer / (meth)acrylate alkyl ester terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / (meth)acrylate alkyl ester / carbonyl terpolymers, methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene / vinyl acetate), polybutadiene, polyisoprene, styrene-based block copolymers, polyacrylonitrile, organosilicon, and any combination thereof.

[0149] Clause 10. The method according to Clause 1, wherein at least some of the OACTP particles have voids, the voids containing the emulsion stabilizer at the void / thermoplastic polymer interface.

[0150] Clause 11. The method according to Clause 10, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises nanoparticles and the nanoparticles are embedded in the void / polymer interface.

[0151] Clause 12. The method according to Clause 10, wherein the void contains the fluid-carrying agent.

[0152] Clause 13. The method according to Clause 1, wherein the OACTP particles further include elongated structures on the surface of the OACTP particles, wherein the elongated structures comprise the thermoplastic polymer and the emulsion stabilizer (when included) is associated with the outer surface of the elongated structures.

[0153] Clause 14. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering less than 5% of the surface of the OACTP particles.

[0154] Clause 15. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 5% of the surface of the OACTP particles.

[0155] Clause 16. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 25% of the surface of the OACTP particles.

[0156] Clause 17. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 50% of the surface of the OACTP particles.

[0157] Clause 18. The method according to Clause 1, wherein the thermoplastic polymer is present in the mixture at a weight percentage of 5% to 60% by weight.

[0158] Clause 19. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present in the mixture at a weight percentage of 0.05% to 5% by weight of the thermoplastic polymer.

[0159] Clause 20. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises nanoparticles with an average diameter of 1 nm to 500 nm.

[0160] Clause 21. The method according to Clause 1, wherein the carrier fluid is selected from: silicone oil, fluorinated silicone oil, perfluorinated silicone oil, polyethylene glycol, alkyl-terminated polyethylene glycol (e.g., C1-C4 terminal alkyl, such as tetraethylene glycol dimethyl ether (TDG)), alkanes, liquid petrolatum, vison oil, turtle oil, soybean oil, perhydrosqualene, sweet almond oil, calophyllum oil, palm oil, parleam oil, grapeseed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, almond oil, castor oil, avocado oil, jojoba oil, olive oil, cereal germ oil, esters of lanolic acid, esters of oleic acid, esters of lauric acid, esters of stearic acid, fatty acid esters, higher fatty acids, fatty alcohols, polysiloxanes modified with fatty acids, polysiloxanes modified with fatty alcohols, polysiloxanes modified with polyoxyethylene, and any combination thereof.

[0161] Clause 22. The method according to Clause 21, wherein the silicone oil is selected from: polydimethylsiloxane, methylphenyl polysiloxane, alkyl-modified polydimethylsiloxane, alkyl-modified methylphenyl polysiloxane, amino-modified polydimethylsiloxane, amino-modified methylphenyl polysiloxane, fluorinated polydimethylsiloxane, fluorinated methylphenyl polysiloxane, polyether-modified polydimethylsiloxane, polyether-modified methylphenyl polysiloxane, and any combination thereof.

[0162] Clause 23. The method according to Clause 1, wherein the carrier fluid has a viscosity of 1,000 cSt to 150,000 cSt at 25°C.

[0163] Clause 24. The method according to Clause 1, wherein the fluid carrier has a concentration of 0.6 g / cm³. 3 Up to 1.5g / cm 3 The density.

[0164] Clause 25. The method according to Clause 1, wherein mixing is carried out in an extruder.

[0165] Clause 26. The method according to Clause 1, wherein mixing is carried out in a stirred reactor.

[0166] Clause 27. The method according to Clause 1, wherein the emulsion stabilizer comprises a surfactant.

[0167] Clause 28. According to the method of Clause 1, said OACTP particles have a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm, and a D90 of about 3 μm to about 300 μm, wherein D10... <D50<D90。

[0168] Clause 29. The method according to Clause 1, wherein the OACTP particles have a diameter span of about 0.2 to about 10.

[0169] Clause 30. According to the method of Clause 1, said OACTP particles have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and a D90 of about 70 μm to about 120 μm, wherein D10... <D50<D90。

[0170] Clause 31. The method according to Clause 30, wherein the OACTP particles have a diameter span of about 1.0 to about 2.5.

[0171] Clause 32. According to the method of Clause 1, the OACTP particles have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about 110 μm, and a D90 of about 110 μm to about 175 μm, wherein the D10... <D50<D90。

[0172] Clause 33. The method according to Clause 32, wherein the OACTP particles have a diameter span of about 0.6 to about 1.5.

[0173] Clause 34. According to the method of Clause 1, said OACTP particles have a D10 of about 75 μm to about 125 μm, a D50 of about 100 μm to about 200 μm, and a D90 of about 125 μm to about 300 μm, wherein D10... <D50<D90。

[0174] Clause 35. The method according to Clause 34, wherein the OACTP particles have a diameter span of about 0.2 to about 1.2.

[0175] Clause 36. The method according to Clause 1, wherein the OACTP particles have a roundness of about 0.90 to about 1.0.

[0176] Clause 37. The method according to Clause 1, wherein the OACTP particles have a Hausner ratio of about 1.0 to about 1.5.

[0177] Clause 38. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture and comprises nanoparticles, and wherein the nanoparticles comprise oxide nanoparticles.

[0178] Clause 39. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture and comprises nanoparticles, and wherein the nanoparticles comprise carbon black.

[0179] Clause 40. The method according to Clause 1, wherein the emulsion stabilizer is contained in the mixture and comprises nanoparticles, and wherein the nanoparticles comprise polymer nanoparticles.

[0180] Clause 41. A composition comprising: light-absorbing thermoplastic polymer particles (OACTP particles) containing a thermoplastic polymer and a light-absorbing agent non-covalently bonded to the thermoplastic polymer, wherein the particles have a sphericity of about 0.90 to about 1.0.

[0181] Clause 42. The composition according to Clause 41, wherein the OACTP particles contain 0.01% to 30% by weight of the light absorber based on the weight of the thermoplastic polymer in the OACTP particles.

[0182] Clause 43. The composition according to Clause 41, wherein the light absorber is selected from the family: rhodamine, fluorescein, coumarin, naphthalenedicarboximide, benzoxanthracene, acridine, cyanine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polyacetylenes, triarylmethane, anthraquinone, pyrazolone, quinophthalone, carbonyl dyes, diazo dyes, phenanthrone, pyrrolopyrroledione (DPP), dioxazine dyes, phthalocyanine, indigo anthraquinone, benzoxanthrone, violet anthraquinone, azo dyes, phthalocyanine dyes, quinacridone dyes, anthraquinone dyes, indigo dyes, thio-indigo dyes, pyrenone dyes, dinaphthalene-phenylene dyes, isoindole dyes, aromatic amino acids, flavins, pyridoxine derivatives, chlorophyll derivatives, and any combination thereof.

[0183] Clause 44. The composition according to Clause 41, wherein the OACTP particles further comprise an emulsion stabilizer associated with the outer surface of the OACTP particles.

[0184] Clause 45. The composition according to Clause 41, wherein the OACTP particles further comprise an emulsion stabilizer, and wherein at least some of the OACTP particles have voids that contain the emulsion stabilizer at the void / polymer interface.

[0185] Clause 46. The composition according to Clause 45, wherein the emulsion stabilizer comprises nanoparticles and the nanoparticles are embedded in the void / polymer interface.

[0186] Clause 47. The composition according to Clause 45, wherein the void contains a fluid-carrying agent.

[0187] Clause 48. The composition according to Clause 44, wherein the OACTP particles further include elongated structures on the surface of the OACTP particles, wherein the elongated structures comprise the thermoplastic polymer and the emulsion stabilizer is associated with the outer surface of the elongated structures.

[0188] Clause 49. The composition according to Clause 44, wherein the emulsion stabilizer forms a coating that covers less than 5% of the surface of the OACTP particles.

[0189] Clause 50. The composition according to Clause 44, wherein the emulsion stabilizer forms a coating that covers at least 5% of the surface of the OACTP particles.

[0190] Clause 51. The composition according to Clause 44, wherein the emulsion stabilizer forms a coating that covers at least 25% of the surface of the OACTP particles.

[0191] Clause 52. The composition according to Clause 44, wherein the emulsion stabilizer forms a coating that covers at least 50% of the surface of the OACTP particles.

[0192] Clause 53. The composition according to Clause 44, wherein the emulsion stabilizer comprises nanoparticles having an average diameter of 1 nm to 500 nm.

[0193] Clause 54. The composition according to Clause 41, wherein the OACTP particles have a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm, and a D90 of about 3 μm to about 300 μm, wherein the D10 <D50<D90。

[0194] Clause 55. The composition according to Clause 41, wherein the OACTP particles have a diameter span of about 0.2 to about 10.

[0195] Clause 56. The composition according to Clause 41, wherein the OACTP particles have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and a D90 of about 70 μm to about 120 μm, wherein the D10 <D50<D90。

[0196] Clause 57. The composition according to Clause 56, wherein the OACTP particles have a diameter span of about 1.0 to about 2.5.

[0197] Clause 58. The composition according to Clause 41, wherein the OACTP particles have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about 110 μm, and a D90 of about 110 μm to about 175 μm, wherein the D10 <D50<D90。

[0198] Clause 59. The composition according to Clause 58, wherein the OACTP particles have a diameter span of about 0.6 to about 1.5.

[0199] Clause 60. The composition according to Clause 41, wherein the OACTP particles have a D10 of about 75 μm to about 125 μm, a D50 of about 100 μm to about 200 μm, and a D90 of about 125 μm to about 300 μm, wherein the D10 <D50<D90。

[0200] Clause 61. The composition according to Clause 60, wherein the OACTP particles have a diameter span of about 0.2 to about 1.2.

[0201] Clause 62. The composition according to Clause 41, wherein the OACTP particles have a Hausner ratio of about 1.0 to about 1.5.

[0202] Clause 63. A method comprising: depositing OACTP particles, optionally combined with other thermoplastic polymer particles, in a specified shape onto a surface; and, once deposited, heating at least a portion of the particles to promote their consolidation to form a consolidated body.

[0203] Clause 64. A method comprising: mixing a mixture comprising the thermoplastic polymer, the carrier fluid immiscible with the thermoplastic polymer, a light absorber, and optionally an emulsion stabilizer, at a temperature greater than the melting point or softening temperature of the thermoplastic polymer and at a shear rate sufficiently high to disperse the thermoplastic polymer in a carrier fluid; cooling the mixture to below the melting point or softening temperature of the thermoplastic polymer to form solidified thermoplastic polymer particles containing the light absorber (OACTP particles), the solidified thermoplastic polymer particles containing the light absorber comprising the thermoplastic polymer and the light absorber; and separating the solidified OACTP particles from the carrier fluid.

[0204] Clause 65. The method according to Clause 64, wherein the OACTP particles contain 0.01% to 30% by weight of the light absorber based on the weight of the thermoplastic polymer in the OACTP particles.

[0205] Clause 66. The method according to Clause 64, wherein the light absorber is selected from: rhodamine, fluorescein, coumarin, naphthalenedicarboximide, benzoxanthracene, acridine, cyanine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polyacetylenes, triarylmethane, anthraquinone, pyrazolone, quinophthalone, carbonyl dyes, diazo dyes, phenanthrone, pyrrolopyrroledione (DPP), dioxazine dyes, phthalocyanine, indigoanthraquinone, benzoanthraquinone, violetanthraquinone, azo dyes, phthalocyanine dyes, quinacridone dyes, anthraquinone dyes, indigo dyes, thio-indigo dyes, pyrenone dyes, dinaphthalene-phenylene dyes, isoindole dyes, aromatic amino acids, flavins, pyridoxine derivatives, chlorophyll derivatives, and any combination thereof.

[0206] Clause 67. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises a surfactant and / or nanoparticles.

[0207] Clause 68. The method according to Clause 67, wherein the emulsion stabilizer associates with the outer surface of the OACTP particles.

[0208] Clause 69. The method according to Clause 68, wherein the emulsion stabilizer is embedded in the outer surface.

[0209] Clause 70. The thermoplastic polymer described according to Clause 64 is selected from: polyamide, polyurethane, polyethylene, polypropylene, polyacetal, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene terephthalate (PTT), polyhexane terephthalate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyester (e.g., polylactic acid), polyether, polyethersulfone, polyetheretherketone, polyacrylate, polymethacrylate, polyimide, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide, vinyl polymers, polyaryl ethers, polyarylene sulfides, polysulfone, polyetherketone, polyamide-imide, polyetherimide, polyether ester, copolymers comprising polyether blocks and polyamide blocks (PEBA or polyether block amide), grafted or ungrafted thermoplastics. Polyolefins, functionalized or unfunctionalized ethylene / vinyl monomer polymers, functionalized or unfunctionalized ethylene / (meth)acrylate alkyl esters, functionalized or unfunctionalized (meth)acrylate polymers, functionalized or unfunctionalized ethylene / vinyl monomer / (meth)acrylate alkyl ester terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / (meth)acrylate alkyl ester / carbonyl terpolymers, methyl methacrylate-butadiene-styrene (MBS) type core-shell polymers, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene / vinyl acetate), polybutadiene, polyisoprene, styrene-based block copolymers, polyacrylonitrile, organosilicon, and any combination thereof.

[0210] Clause 71. The method according to Clause 64, wherein at least some of the OACTP particles have voids, the voids containing the emulsion stabilizer at the void / thermoplastic polymer interface.

[0211] Clause 72. The method according to Clause 71, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises nanoparticles and the nanoparticles are embedded in the void / polymer interface.

[0212] Clause 73. The method according to Clause 71, wherein the void contains the fluid-carrying fluid.

[0213] Clause 74. The method according to Clause 64, wherein the OACTP particles further include elongated structures on the surface of the OACTP particles, wherein the elongated structures contain the thermoplastic polymer and the emulsion stabilizer (when included) is associated with the outer surface of the elongated structures.

[0214] Clause 75. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering less than 5% of the surface of the OACTP particles.

[0215] Clause 76. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 5% of the surface of the OACTP particles.

[0216] Clause 77. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 25% of the surface of the OACTP particles.

[0217] Clause 78. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present and forms a coating covering at least 50% of the surface of the OACTP particles.

[0218] Clause 79. The method according to Clause 64, wherein the thermoplastic polymer is present in the mixture at a weight of 5% to 60% by weight.

[0219] Clause 80. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer is present in the mixture at a weight percentage of 0.05% to 5% by weight of the thermoplastic polymer.

[0220] Clause 81. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture, and wherein the emulsion stabilizer comprises nanoparticles with an average diameter of 1 nm to 500 nm.

[0221] Clause 82. The method according to Clause 64, wherein the carrier fluid is selected from: silicone oil, fluorinated silicone oil, perfluorinated silicone oil, polyethylene glycol, alkyl-terminated polyethylene glycol (e.g., C1-C4 terminal alkyl, such as tetraethylene glycol dimethyl ether (TDG)), alkanes, liquid petrolatum, vison oil, turtle oil, soybean oil, perhydrosqualene, sweet almond oil, calophyllum oil, palm oil, parleam oil, grapeseed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, almond oil, castor oil, avocado oil, jojoba oil, olive oil, cereal germ oil, esters of lanolic acid, esters of oleic acid, esters of lauric acid, esters of stearic acid, fatty acid esters, higher fatty acids, fatty alcohols, fatty acid-modified polysiloxanes, fatty alcohol-modified polysiloxanes, polyoxyethylene-modified polysiloxanes, and any combination thereof.

[0222] Clause 83. The method according to Clause 82, wherein the silicone oil is selected from: polydimethylsiloxane, methylphenyl polysiloxane, alkyl-modified polydimethylsiloxane, alkyl-modified methylphenyl polysiloxane, amino-modified polydimethylsiloxane, amino-modified methylphenyl polysiloxane, fluorinated polydimethylsiloxane, fluorinated methylphenyl polysiloxane, polyether-modified polydimethylsiloxane, polyether-modified methylphenyl polysiloxane, and any combination thereof.

[0223] Clause 84. The method according to Clause 64, wherein the carrier fluid has a viscosity of 1,000 cSt to 150,000 cSt at 25°C.

[0224] Clause 85. The method according to Clause 64, wherein the carrier fluid has a concentration of 0.6 g / cm³. 3 Up to 1.5g / cm 3 The density.

[0225] Clause 86. The method according to Clause 64, wherein mixing is carried out in an extruder.

[0226] Clause 87. The method according to Clause 64, wherein mixing is carried out in a stirred reactor.

[0227] Clause 88. The method according to Clause 64, comprising the emulsion stabilizer and comprising a surfactant.

[0228] Clause 89. The method according to Clause 64, wherein the OACTP particles have a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm, and a D90 of about 3 μm to about 300 μm, wherein the D10 <D50<D90。

[0229] Clause 90. The method according to Clause 64, wherein the OACTP particles have a diameter span of about 0.2 to about 10.

[0230] Clause 91. The method according to Clause 64, wherein the OACTP particles have a D10 of about 5 μm to about 30 μm, a D50 of about 30 μm to about 70 μm, and a D90 of about 70 μm to about 120 μm, wherein the D10 <D50<D90。

[0231] Clause 92. The method according to Clause 91, wherein the OACTP particles have a diameter span of about 1.0 to about 2.5.

[0232] Clause 93. The method according to Clause 64, wherein the OACTP particles have a D10 of about 25 μm to about 60 μm, a D50 of about 60 μm to about 110 μm, and a D90 of about 110 μm to about 175 μm, wherein the D10 <D50<D90。

[0233] Clause 94. The method according to Clause 93, wherein the OACTP particles have a diameter span of about 0.6 to about 1.5.

[0234] Clause 95. The method according to Clause 64, wherein the OACTP particles have a D10 of about 75 μm to about 125 μm, a D50 of about 100 μm to about 200 μm, and a D90 of about 125 μm to about 300 μm, wherein the D10 <D50<D90。

[0235] Clause 96. The method according to Clause 96, wherein the OACTP particles have a diameter span of about 0.2 to about 1.2.

[0236] Clause 97. The method according to Clause 64, wherein the OACTP particles have a roundness of about 0.90 to about 1.0.

[0237] Clause 98. The method according to Clause 64, wherein the OACTP particles have a Hausner ratio of about 1.0 to about 1.5.

[0238] Clause 99. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture and comprises nanoparticles, and wherein the nanoparticles comprise oxide nanoparticles.

[0239] Clause 100. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture and comprises nanoparticles, and wherein the nanoparticles comprise carbon black.

[0240] Clause 101. The method according to Clause 64, wherein the emulsion stabilizer is contained in the mixture and comprises nanoparticles, and wherein the nanoparticles comprise polymer nanoparticles.

[0241] Unless otherwise specified, all figures regarding the quantity of expressed components, properties (such as molecular weight), process conditions, etc., used in this specification and related claims should be understood to be modified by the term "about" in all cases. Therefore, unless stated to the contrary, the numerical parameters listed in the following specification and appended claims are approximations, which may vary depending on the desired properties sought to be obtained according to embodiments of the invention. To a minimum and without attempting to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant digits reported and by applying customary rounding.

[0242] This document presents one or more exemplary embodiments of the invention incorporated herein by reference. For clarity, not all features of the physical implementation are described or illustrated herein. It should be understood that in the development of physical implementations incorporated herein by reference, numerous implementation-specific decisions must be made to achieve the developer’s objectives, such as compliance with system-related constraints, business-related constraints, governmental-related constraints, and other constraints that vary from implementation to implementation and change over time. While the efforts made by the developer may be time-consuming, such efforts will be routine tasks for those skilled in the art who will benefit from this disclosure.

[0243] Although this document describes compositions and methods as “comprising” various components or steps, compositions and methods may also be described as “consisting substantially of various components and steps” or “comprised of various components and steps.”

[0244] To facilitate a better understanding of the embodiments of the present invention, the following preferred or representative embodiments are provided. These embodiments should not be construed as limiting or restricting the scope of the invention.

[0245] Example

[0246] Example 1. Polyamide 12 microparticles were prepared in a 25 mm twin-screw extruder (Werner & Pfleiderer ZSK-25). The carrier fluid was PDMS oil with a viscosity of 10,000 cSt at room temperature. The concentrations of the components in the final mixture in the extruder are provided in Table 3. The polymer pellets were added to the extruder, brought to temperature, and then dispersed therein... Preheated carrier fluid of R812S silica nanoparticles was added to the molten polymer in the extruder. Other operating parameters are provided in Table 1. The mixture was then discharged into a container and allowed to cool to room temperature over several hours. Light scattering particle size data are also provided in Table 1.

[0247] Table 1

[0248]

[0249]

[0250] *Relative to the total combined weight of PDMS oil and polyamide

[0251] **Compared to polyamide

[0252] Example 2 (Hypothetical Example). The polyamide 12 microparticles from Table 1, or polyamide 12 microparticles obtained by other melt emulsification methods, can be dispersed in methanol with a solids loading of approximately 20% by weight (20 g of polyamide 12 microparticles dissolved in 80 g of methanol). Once the particles are wetted, a solution of 0.2% by weight of fluorescein in water can be added to the particle slurry, and mixing can continue at ambient temperature. In this example, heating should be avoided as it can lead to a decrease in hydrogen bond strength. After mixing at 150 rpm (stirring rod, beaker) for approximately 4 hours, the particles can be filtered from the methanol and dried overnight in an oven at 40°C.

[0253] Without being bound by theory, it is believed that the amine groups of polyamide 12 will hydrogen-bond with various oxygen-containing groups of fluorescein. Furthermore, since polyamide 12 is exposed to fluorescein after the formation of polymer particles, it is believed that fluorescein will be mainly located on or near the surface of the polymer particles.

[0254] The fluorescence spectrum of polyamide 12 microparticles can be measured by fluorescence microscopy. When excited at 495 nm, fluorescence microscopy shows an emission maximum at 515 nm, which is a typical fluorescence peak of the open-ring form of fluorescein.

[0255] These fluorescein polyamide 12 microparticles can be selectively sintered and printed, allowing for re-examination of fluorescence. The melting point and decomposition temperature of fluorescein are approximately 315°C. The sintering process will not reach this temperature, thus negating its fluorescent properties.

[0256] Therefore, the present invention is well-suited to achieving the stated objectives and advantages, as well as those inherent therein. The specific embodiments disclosed above are merely exemplary, as the invention may be modified and practiced in different but equivalent ways that will be apparent to those skilled in the art who benefit from the teachings herein. Furthermore, no limitation is contemplated on the details of the constructions or designs shown herein, except as set forth in the following claims. Therefore, it is apparent that the specific exemplary embodiments disclosed above may be altered, combined, or modified, and all such changes are considered to be within the scope and spirit of the invention. The invention disclosed herein by way of example may be practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein. While compositions and methods are described as “comprising,” “containing,” or “including” various components or steps, compositions and methods may also be “substantially composed of various components and steps” or “composed of various components and steps.” All figures and ranges disclosed above may vary in quantity. Whenever a numerical range with a lower and upper limit is disclosed, any quantity falling within that range and any included range is specifically disclosed. Specifically, each range of values ​​disclosed herein (in the form of "about a to about b", or equivalently, "approximately a to b", or equivalently, "approximately ab") should be understood to describe every numerical value and range covered within a wider range of values. Furthermore, the terms in the claims have their ordinary, common meaning unless otherwise explicitly and clearly defined by the patentee. Additionally, the indefinite articles "an" or "a" used in the claims are defined herein as meaning that the element described has one or more elements.

Claims

1. A method, the method comprising: A mixture comprising the thermoplastic polymer, the carrier fluid immiscible with the thermoplastic polymer, and an emulsion stabilizer, wherein the emulsion stabilizer comprises nanoparticles, is mixed at a temperature greater than the melting point or softening temperature of the thermoplastic polymer and at a sufficiently high shear rate to disperse the thermoplastic polymer in the carrier fluid. The mixture is cooled to below the melting point or softening temperature of the thermoplastic polymer to form solidified particles containing the thermoplastic polymer. Separating the solidified particles from the carrier fluid; and The solidified particles are exposed to a light absorber to produce thermoplastic polymer particles containing the light absorber, referred to as OACTP particles. The carrier fluid has a viscosity of 1,000 cSt to 150,000 cSt at 25°C, and The emulsion stabilizer associates with the outer surface of the OACTP particles and is embedded in the outer surface.

2. The method according to claim 1, wherein the light absorber is a first light absorber, and wherein the mixture further comprises a second light absorber.

3. The method according to claim 2, wherein the first light absorber and the second light absorber are different.

4. The method of claim 1, wherein the OACTP particles contain 0.01% to 30% by weight of the light absorber, based on the weight of the thermoplastic polymer in the OACTP particles.

5. The method according to claim 1, wherein the light absorber is selected from: coumarin, naphthalenedicarboximide, benzoxanthracene, acridine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polyacetylenes, triarylmethane, pyrazolone, quinophthalone, carbonyl dyes, phenanthrene, pyrrolopyrroledione, dioxazine dyes, azo dyes, phthalocyanine dyes, quinacridone dyes, anthraquinone dyes, indigo dyes, thio-indigo dyes, pyrenone dyes, dinaphthalene-phenylene dyes, isoindole dyes, aromatic amino acids, flavins, pyridoxyl derivatives, chlorophyll derivatives, and any combination thereof.

6. The method according to claim 1, wherein the light absorber is selected from: rhodamine, fluorescein, anthocyanin, diazo dyes, indigoanthraquinone, benzanthraquinone, and violetanthraquinone.

7. The method according to claim 1, wherein the thermoplastic polymer is selected from: polyamide, polyurethane, polyacetal, polycarbonate, polystyrene, polytetrafluoroethylene, polyester, polylactic acid, polyether, polyethersulfone, polyetheretherketone, polyacrylate, polymethacrylate, polyimide, polyphenylene sulfide, polyarylene ether, polyarylene sulfide, polysulfone, polyetherketone, polyamide-imide, polyetherimide, polyether ester, copolymers comprising polyether blocks and polyamide blocks, grafted or ungrafted thermoplastic polyolefins, functionalized or unfunctionalized ethylene / (meth)acrylate alkyl esters, functionalized or unfunctionalized (meth)acrylate polymers, functionalized or unfunctionalized ethylene / vinyl monomer / (meth)acrylate alkyl ester terpolymers, ethylene / vinyl monomer / carbonyl terpolymers, ethylene / (meth)acrylate alkyl ester / carbonyl terpolymers, chlorinated or chlorosulfonated polyethylene, polyvinylidene fluoride, phenolic resins, styrene-based block copolymers, polyacrylonitrile, organosilicon, and any combination thereof.

8. The method according to claim 1, wherein the thermoplastic polymer is selected from functionalized or non-functionalized ethylene / vinyl monomer polymers.

9. The method of claim 1, wherein the thermoplastic polymer is selected from vinyl polymers.

10. The method according to claim 1, wherein the thermoplastic polymer is selected from: polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polyhexane terephthalate, acrylonitrile butadiene styrene, methyl methacrylate-butadiene-styrene core-shell polymer, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) block terpolymer, polyvinyl chloride, poly(ethylene / vinyl acetate), polyethylene, polypropylene, polybutadiene, and polyisoprene.

11. The method of claim 1, wherein the OACTP particles have a D10 of 0.1 µm to 125 µm, a D50 of 0.5 µm to 200 µm, and a D90 of 3 µm to 300 µm, wherein the D10 <D50<D90。 12. The method of claim 1, wherein the OACTP particles have a diameter span of 0.2 to 10.

13. The method of claim 1, wherein the OACTP particles have a roundness of 0.90 to 1.

0.

14. The method of claim 1, wherein the OACTP particles have a Hausner ratio of 1.0 to 1.

5.

15. A method comprising: A mixture comprising the thermoplastic polymer, the carrier fluid immiscible with the thermoplastic polymer, a light absorber, and an emulsion stabilizer is mixed at a temperature greater than the melting point or softening temperature of the thermoplastic polymer and at a sufficiently high shear rate to disperse the thermoplastic polymer in the carrier fluid, wherein the emulsion stabilizer comprises nanoparticles. The mixture is cooled below the melting point or softening temperature of the thermoplastic polymer to form solidified thermoplastic polymer particles containing a light absorber, referred to as OACTP particles, the solidified thermoplastic polymer particles containing the light absorber comprising the thermoplastic polymer and the light absorber; and The solidified OACTP particles are separated from the carrier fluid. The carrier fluid has a viscosity of 1,000 cSt to 150,000 cSt at 25°C, and The emulsion stabilizer associates with the outer surface of the OACTP particles and is embedded in the outer surface.

16. The method of claim 15, wherein the OACTP particles contain 0.01% to 30% by weight of the light absorber, based on the weight of the thermoplastic polymer in the OACTP particles.

17. The method according to claim 15, wherein the light absorber is selected from: coumarin, naphthalenedicarboximide, benzoxanthracene, acridine, oxazine, phenanthridine, pyrrolidone, benzaldehyde, polyacetylenes, triarylmethane, pyrazolone, quinophthalone, carbonyl dyes, phenanthrene, pyrrolopyrroledione, dioxazine dyes, azo dyes, phthalocyanine dyes, quinacridone dyes, anthraquinone dyes, indigo dyes, thio-indigo dyes, pyrenone dyes, dinaphthalene-phenylene dyes, isoindole dyes, aromatic amino acids, flavins, pyridoxyl derivatives, chlorophyll derivatives, and any combination thereof.

18. The method according to claim 15, wherein the light absorber is selected from: rhodamine, fluorescein, anthocyanin, diazo dyes, indigoanthraquinone, benzanthraquinone, and violetanthraquinone.

19. A composition prepared by the method of claim 1, the composition comprising: thermoplastic polymer particles containing a thermoplastic polymer and a light absorber non-covalently bonded to said thermoplastic polymer, referred to as OACTP particles, wherein said particles have a sphericity of 0.90 to 1.

0. The OACTP particles contain an emulsion stabilizer located on the outer surface of the particles, and the emulsion stabilizer comprises nanoparticles. The emulsion stabilizer associates with the outer surface of the OACTP particles and is embedded in the outer surface.

20. A method, the method comprising: The OACTP particles according to claim 19 may optionally be combined with other thermoplastic polymer particles and deposited on the surface in a specified shape; as well as Once deposited, at least a portion of the particles are heated to promote their consolidation and form a solidified body.

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