WO2020139824A1 - Poudre polyoléfinique pour frittage sélectif au laser - Google Patents

Poudre polyoléfinique pour frittage sélectif au laser Download PDF

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Publication number
WO2020139824A1
WO2020139824A1 PCT/US2019/068304 US2019068304W WO2020139824A1 WO 2020139824 A1 WO2020139824 A1 WO 2020139824A1 US 2019068304 W US2019068304 W US 2019068304W WO 2020139824 A1 WO2020139824 A1 WO 2020139824A1
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WO
WIPO (PCT)
Prior art keywords
polyolefin
polyolefin powder
powder
selective laser
particles
Prior art date
Application number
PCT/US2019/068304
Other languages
English (en)
Inventor
Alexandre DA LUZ
Alessandro Bernardi
Marcelo FARAH
Original Assignee
Braskem America, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Braskem America, Inc. filed Critical Braskem America, Inc.
Publication of WO2020139824A1 publication Critical patent/WO2020139824A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Definitions

  • the disclosed subject matter relates to polyolefin powders and three dimensional (3D) printed parts made therefrom.
  • SLS selective laser sintering
  • AM additive manufacturing
  • PSD small particle size distribution
  • using powdered material with a small particle size in industrial processes can lead to powder transport, compaction, fluidization, vessel discharge, filter clogging, drag of the particles by transition points (reactor top), extruder feeding, etc. Accordingly, an opportunity to develop alternative powders remains.
  • a polyolefin powder is provided.
  • the polyolefin powder includes a polyolefin polymer.
  • the polyolefin may be selected from polypropylene,
  • the polyolefin may have bimodal, multimodal, or broad molecular weight distribution.
  • the polyolefin powder is not milled.
  • particles in the polyolefin powder can be a spherical, semi-spherical, potato-type, and/or an irregular shape. The shape can be defined by an aspect ratio between the maximum diameter to the minimal diameter.
  • the aspect ratio can be from 1 to 2.
  • the polyolefin powder has porous particles.
  • the porous particles have a volume of pores in the range of about 0.001 to about 0.100 cm 3 /g.
  • the polyolefin powder can have a particle size distribution (PSD) of from about 5 microns to about 1000 microns.
  • a three dimensional (3D) part made from a polyolefin powder is provided.
  • the part can be produced by selective laser sintering or selective laser melting using a polyolefin polymer.
  • the polyolefin polymer can be polyethylene, polypropylene, or a mixture thereof.
  • the part can be characterized as having low porosity, good particle diffusion, high bulk density, and/or good mechanical properties.
  • FIGS. 1A-1C are microscopic images of powders.
  • FIG. 1A shows spherical particles;
  • FIG. IB shows“potato-type” particles; and
  • FIG. 1C shows particles made by cryogenic grinding.
  • FIGS. 2A-2D are micrographic images of polyolefin powder particles, in accordance with some embodiments described herein.
  • FIGS. 3 A and 3B are micrographic images of a part printed with polypropylene particles.
  • FIGS. 4A and 4B are micrographic images of parts printed with polyolefin powder particles, in accordance with some embodiments described herein.
  • FIGS. 5A-5D are perspective images of parts printed with polyolefin powder particles, in accordance with some embodiments described herein.
  • a polyolefin powder is provided.
  • the polyolefin may be selected from polypropylene, polyethylene, propylene copolymers, or ethylene copolymers, including, for example, ethylene vinyl acetate, and combinations thereof.
  • the polyolefins may include homopolymers, random copolymers, block copolymers, and heterophasic polymer compositions such as impact copolymers.
  • the polyolefin powder can be produced by a process comprising a catalyst.
  • the catalyst can be or include any suitable material.
  • the catalyst is a heterogeneous supported catalyst.
  • the catalyst is a homogeneous catalyst.
  • a co catalyst is used.
  • a carrier is used.
  • the supported catalyst has a spherical, semi-spherical, potato-type, or irregular shape.
  • the catalyst and/or co-catalyst is a metal.
  • the metal is titanium, aluminum, zirconium, hafnium, or any other suitable metal.
  • a Ziegler-Natta or Ziegler-Natta-type catalyst is used.
  • the support can be any suitable material.
  • the support is a metal. In some embodiments, for example, the support includes magnesium or another suitable metal. In some embodiments, the carrier has a specifically defined size and shape. In some embodiments, for example, the carrier has a spherical, semi-spherical, potato-type, or irregular shape. In some embodiments, additional components are used. The additional components can be organic or inorganic materials. In some embodiments, for example, an additional component is used to modify the polymerization reaction.
  • the polyolefin may have bimodal, multimodal, or broad molecular weight distribution.
  • the molecular weight distribution can affect the sintering or melting processes, and ultimately the mechanical properties of a printed part.
  • Lower molecular weight polymers may present good flowability and melt viscosity that would favor the coalescence of particles in selective laser sintering (SLS) or selective laser melting (SLM) processes.
  • SLS selective laser sintering
  • SLM selective laser melting
  • higher molecular weight polymers would favor the mechanical properties of the printed part; however, the poor diffusion of the high molecular weight chains could affect the coalescence of the particles resulting in fragile parts.
  • the combination of different molecular weights could favor the coalescence of particles resulting in parts with better mechanical properties.
  • the low molecular weight chains could act as a lubricant for the high molecular weight chains, and improve the coalescence of particles.
  • a high molecular weight could yield one or more advantageous mechanical properties.
  • the polyolefin powder is not milled.
  • particles in the polyolefin powder can have any suitable shape.
  • a particle in the polyolefin powder can have a spherical, semi-spherical, potato-type, or irregular shape.
  • the polyolefin powder may comprise particles having the same shape or different shapes.
  • a substantial amount of the particles in the polyolefin powder have the same shape.
  • the aspect ratio for the particles is from about 1 to about 2, from about 1 to about 1.8, from about 1 to about 1.5, from about 1 to about 1.4, from about 1 to about 1.3, from about 1 to about 1.2, or from about 1 to about 1.1.
  • the polyolefin powder has porous particles.
  • the porous particles have a volume of pores in the range of about 0.001 to about 0.100 cmVg, from 0.002 to about 0.050 cmVg, from about 0.004 to about 0.010 cmVg.
  • the porous particles may facilitate the absorption of energy, which would favor melting, diffusion, and coalescence of the particles.
  • the polyolefin powder can have a particle size distribution (PSD) of from about 5 microns to about 1000 microns, from about 50 to about 500 microns, from about 75 to about 400 microns, from about 90 to about 350 microns, from about 90 to about 250 microns, from about 100 to about 230 microns, from about 100 to about 200 microns, from about 105 to about 195 microns, from about 100 to about 170 microns, from about 100 to about 150 microns, or from about 100 to about 130 microns.
  • the PSD is from about 3 microns to about 600 microns, or from about 15 microns to about 450 microns, or from about 30 microns to about 300 microns.
  • the polyolefin powder of the present application may be used to produce three dimensional (3D) parts by additive manufacturing techniques such as selective laser sintering or selective laser melting.
  • the 3D printed part can have nearly any structure and/or configuration. Generally, properties of a printed part will vary depending on the particular polymer powder used to produce it and the conditions employed during the selective laser sintering or selective laser melting process.
  • the 3D printed part can be characterized by its level of porosity, surface area, diffusion among particles, bulk density, and/or mechanical properties. The morphology and shape of a polyolefin powder will affect the properties of the 3D printed part.
  • parts produced with a polyolefin powder of the present application can be characterized as having low porosity, good particle diffusion, high bulk density, and/or good mechanical properties.
  • particle size and particle shape can be adjusted to improve the compatibility or workability of the polyolefin powder. Without being bound to a particular theory, particle size and shape will generally effect the available contact points on the particle for sintering during the selective laser sintering process.
  • a process for printing a 3D part comprises the steps of (a) disposing a layer of a polyolefin powder on a target surface; (b) directing an energy beam over a selected area of the polyolefin powder layer, in which the powder is sintered or melted; and (c) repeating said steps (a) and (b) to form the 3D part.
  • a 3D part with lower porosity is obtained.
  • a 3D part with good diffusion among particles is obtained.
  • a 3D part with high bulk density, or good mechanical properties is obtained.
  • the 3D printed part is characterized by a bulk density of at least about 0.30 g/cm 3 , of at least about 0.50 g/cm 3 , of at least about 0.80 g/cm 3 , or of at least about 1.0 g/cm 3 .
  • the ratio of the bulk density of the 3D printed part to the bulk density of the polyolefin ranges from about 0.5 to 1, about 0.65 to 1, or about 0.85 to 1.
  • the part demonstrates mechanical properties that are about 30% higher than that for a part prepared by injection molding. In some embodiments, the part demonstrates mechanical properties that are about 50% higher than that for a part prepared by injection molding. In some embodiments, the part demonstrates mechanical properties that are about 80% higher than that for a part prepared by injection molding. In some embodiments, the part demonstrates mechanical properties that are about 90% higher than that for a part prepared by injection molding.
  • Inventive Example a polyethylene powder was produced using a Ziegler-Natta- type catalyst in a Hostalen Technology process.
  • the polyethylene powder was a high density polyethylene (HDPE) with a density of 0.953 g/cm 3 (measured according ASTM D792), a MFI (melt flow index) of 0.33 g/10 min (measured at 190°C at 5kg according to ASTM D1238) with a bimodal molecular weight distribution.
  • the volume of pores and surface area for the particles were determined to be 0.004 to 0.010 cm 3 /g and 0.5 m 2 /g, respectively. No milling process or post-reactor treatment was conducted on the particles.
  • the HDPE contains a broad particle size distribution in which the particle sizes vary from about 30 pm to about 200 pm.
  • the figures show the presence of porous particles, and particles having spherical, semi-spherical, irregular, or a potato-type shapes.
  • Comparative Example a commercially available micronized polypropylene having a narrow particle size distribution in which the particle sizes vary from about 30 pm to about 50 pm.
  • the polyolefin powders from the inventive and comparative examples were used in a selective laser sintering process to produce 3D printed parts. After printing, a red dye was added to the parts to highlight the morphology of their surfaces.
  • Figures 3 A and 3B show micrographies of a part printed with the commercially available micronized polypropylene according to the comparative example.
  • the figures show sintering among the particles; however, the particles have maintained most of their spherical morphology, which indicates poor coalescence between the particles.
  • the parts have high porosity. This effect may be due to sintering in a solid or semisolid state. It would be expected that the presence of pores in the printed part may affect its mechanical properties.
  • Figures 4A-4B show micrographies of a part printed with the HDPE powder according to the inventive example.
  • the part has a smooth surface and low porosity.
  • the volume of pores and the surface area for the printed parts were determined to be 0.000024 cm 3 /g and 0.05 m 2 /g, respectively.
  • a reduction in surface area of 10 times and a reduction in porosity of about 300 times were observed for the printed part.
  • Figures 5A-5D show parts produced with the HDPE powder according to the inventive example. As can be seen from the figures, the parts have unique structures and complex configurations. The parts demonstrated excellent mechanical properties. Thus, the inventive example parts demonstrate that polyolefin particles obtained directly from industrial reactors, without milling or any other modification or treatment, can be utilized in a selective layer sintering process to prepare improved parts.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une poudre polyoléfinique comprenant un polymère polyoléfinique. La polyoléfine peut être du polypropylène, du polyéthylène, des copolymères de propylène ou des copolymères d'éthylène, comprenant, par exemple, de l'éthylène-acétate de vinyle et des combinaisons de ceux-ci. La polyoléfine peut avoir une répartition bimodale, multimodale ou large de masses moléculaires. La poudre polyoléfinique n'a pas besoin d'être broyée et les particules dans la poudre polyoléfinique peuvent être sphériques, semi-sphériques, ovales ou de forme irrégulière. La poudre polyoléfinique peut comprendre des particules poreuses. L'invention concerne également une pièce tridimensionnelle (3D) fabriquée à partir de la poudre polyoléfinique. La pièce peut être produite par frittage laser au sélectif ou par fusion sélective au laser.
PCT/US2019/068304 2018-12-28 2019-12-23 Poudre polyoléfinique pour frittage sélectif au laser WO2020139824A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862785772P 2018-12-28 2018-12-28
US62/785,772 2018-12-28

Publications (1)

Publication Number Publication Date
WO2020139824A1 true WO2020139824A1 (fr) 2020-07-02

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990268A (en) * 1992-11-23 1999-11-23 Dtm Corporation Sinterable semi-crystalline powder and near-fully dense article formed therewith
US20040110853A1 (en) * 2002-08-20 2004-06-10 Wang Louis Chun Process for preparing molded porous articles and the porous articles prepared therefrom
US20060003888A1 (en) * 2004-07-05 2006-01-05 Yuanyi Yang Spheric catalyst component for olefin polymerization and catalyst comprising the same
US20110293918A1 (en) * 2008-12-01 2011-12-01 Rhodia Operations Producing an item by the selective fusion of polymer powder layers
US20110313071A1 (en) * 2004-06-07 2011-12-22 Louis Chun Wang Polyethylene molding powder and porous articles made therefrom
US20130046040A1 (en) * 2010-05-03 2013-02-21 Ticona Llc Polyethylene powders and porous articles produced therefrom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990268A (en) * 1992-11-23 1999-11-23 Dtm Corporation Sinterable semi-crystalline powder and near-fully dense article formed therewith
US20040110853A1 (en) * 2002-08-20 2004-06-10 Wang Louis Chun Process for preparing molded porous articles and the porous articles prepared therefrom
US20110313071A1 (en) * 2004-06-07 2011-12-22 Louis Chun Wang Polyethylene molding powder and porous articles made therefrom
US20060003888A1 (en) * 2004-07-05 2006-01-05 Yuanyi Yang Spheric catalyst component for olefin polymerization and catalyst comprising the same
US20110293918A1 (en) * 2008-12-01 2011-12-01 Rhodia Operations Producing an item by the selective fusion of polymer powder layers
US20130046040A1 (en) * 2010-05-03 2013-02-21 Ticona Llc Polyethylene powders and porous articles produced therefrom

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