US10385478B2 - Process for forming a consumable filament - Google Patents

Process for forming a consumable filament Download PDF

Info

Publication number
US10385478B2
US10385478B2 US16/094,647 US201716094647A US10385478B2 US 10385478 B2 US10385478 B2 US 10385478B2 US 201716094647 A US201716094647 A US 201716094647A US 10385478 B2 US10385478 B2 US 10385478B2
Authority
US
United States
Prior art keywords
filament
propylene
ethylene copolymer
weight
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US16/094,647
Other versions
US20190112732A1 (en
Inventor
Roberto De Palo
Claudio Cavalieri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Poliolefine Italia SRL
Original Assignee
Basell Poliolefine Italia SRL
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 Basell Poliolefine Italia SRL filed Critical Basell Poliolefine Italia SRL
Assigned to Basell Poliolefine Italia, s.r.l. reassignment Basell Poliolefine Italia, s.r.l. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CAVALIERI, CLAUDIO, DE PALO, ROBERTO
Publication of US20190112732A1 publication Critical patent/US20190112732A1/en
Application granted granted Critical
Publication of US10385478B2 publication Critical patent/US10385478B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio

Definitions

  • the present disclosure relates to the field of chemistry. More specifically, the present disclosure relates to polymer chemistry. In particular, the present disclosure relates to a filament made from or containing a propylene ethylene copolymer, for use in an extrusion-based 3D printer.
  • An extrusion-based 3D printer is used to build a 3D model from a digital representation of the 3D model in a layer-by-layer manner by extruding a flowable modeling material.
  • a filament of the modeling material is extruded through an extrusion tip carried by an extrusion head, and is deposited as a sequence of roads on a substrate in an x-y plane.
  • the extruded modeling material fuses to deposited modeling material, and solidifies upon a drop in temperature.
  • the position of the extrusion head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane), and the process is then repeated to form a 3D model resembling the digital representation.
  • Movement of the extrusion head is performed under computer control, in accordance with build data that represents the 3D model.
  • the build data is obtained by slicing the digital representation of the 3D model into multiple horizontally sliced layers. Then, for each sliced layer, the host computer generates a build path for depositing roads of modeling material to form the 3D model.
  • the filament changes the material of the filament, thereby changing the final mechanical and aesthetic properties of the finished object.
  • PVA polylactic acid
  • ABS acrylonitrile, butadiene, styrene
  • polyamides are used for filaments.
  • the filament it is desirable for the filament to have a constant diameter (in some instances, 1.75 mm or 3 mm); otherwise, finely tuning the amount of material in the printed object is challenging. It is difficult to achieve a constant diameter for the filament, which is believed to depend on the characteristics of the polymer.
  • the filament be printable, which, as the term “printable” is used herein, means the filament achieves appropriate adhesion with the plate and among the layers.
  • the present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having:
  • ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %, based upon the weight of the propylene ethylene copolymer;
  • MFR L Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load
  • xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %, based upon the weight of the propylene ethylene copolymer.
  • the FIGURE is a front view of a sample used in print tests.
  • the units of measure are mm. As shown, the printed sample was 5 mm thick.
  • the present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having:
  • ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %; alternatively from about 3.5 wt % to about 10.0 wt %; alternatively from about 3.8 wt % to about 8.0 wt %, based upon the weight of the propylene ethylene copolymer;
  • MFR L Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load
  • xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %; alternatively from about 4 wt % to about 25 wt %, based upon the weight of the propylene ethylene copolymer.
  • copolymer refers to polymer formed from only two monomers: propylene and ethylene.
  • the propylene/ethylene copolymer is extruded in a filament having a constant diameter.
  • the diameter of the filament is about 1.75 mm or about 3 mm. In some embodiments, other diameters are used. In some embodiments, the variation from the nominal diameter is +/ ⁇ 0.05 mm, alternatively +/ ⁇ 0.03 mm. In some embodiments, the diameter of the filament is about 1.75 mm+/ ⁇ 0.05 mm or about 3 mm+/ ⁇ 0.05 mm. In some embodiments, the diameter of the filament is about 1.75 mm+/ ⁇ 0.03 mm or about 3 mm+/ ⁇ 0.03 mm.
  • the polymeric materials when amorphous polymeric materials are used, the polymeric materials have little or no ordered arrangements of their polymer chains in their solid states. It is believed that this lack of arrangements reduces the effects of curling and plastic deformation in the resulting 3D model or support structure.
  • the amorphous polymeric materials are acrylonitrile-butadiene-styrene (ABS) resins or polycarbonate resins.
  • crystalline or semicrystalline polymer can exhibit superior mechanical properties than amorphous polymers
  • crystalline or semicrystalline polymers show undesirable shrinkage effects both when the extruded road is deposited to form a portion of a layer of a 3D model and when the road is cooled.
  • the shrinkage effects renders the crystalline or semicrystalline polymers unsuitable for building 3D objects in an extrusion-based additive manufacturing process.
  • the present disclosure provides a semi-crystalline propylene ethylene copolymer suitable for building a 3D model.
  • propylene ethylene copolymer examples include (a) RP220M sold by LyondellBasell, (b) BOREALIS RD204 CF, and (c) LyondellBasell CLYRELL RC 1908.
  • the filament is made from or contains additionally additives such as antioxidants, slipping agents, process stabilizers, antiacid and nucleants.
  • the filament is made from or contains additionally fillers such as talc, calcium carbonate, wollastonite, glass fibers, glass spheres and carbon derived grades.
  • the filament is made from or contains additionally wood powder, metallic powder, marble powder and similar materials.
  • the Xylene Soluble fraction was measured according to ISO 16152, 2005, but with the following deviations (between parentheses).
  • the solution volume was 250 ml (200 ml).
  • the final drying step was done under vacuum at 70° C. (100° C.).
  • the content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 grams and then, by difference (complementary to 100), the xylene unsoluble %.
  • the peak of the S ⁇ carbon was used as internal reference at 29.9 ppm.
  • the nomenclature was according to C. J. Carman, R. A. Harrington and C. E. Wilkes, “Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode,” 10 Macromolecules 536 (1977).
  • the samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120° C. with a 8% wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
  • E ⁇ ⁇ % ⁇ ⁇ wt . 100 * E ⁇ ⁇ % ⁇ ⁇ mol * M ⁇ ⁇ W E E ⁇ ⁇ % ⁇ ⁇ mol * M ⁇ ⁇ W E + P ⁇ ⁇ % ⁇ ⁇ mol * M ⁇ ⁇ W P
  • the product of reactivity ratio r 1 r 2 was calculated according to Carman (C. J. Carman, R. A. Harrington and C. E. Wilkes, 10 Macromolecules 536 (1977)) as:
  • the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmT ⁇ (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm)
  • the melt flow rate MFR of the polymer was determined according to ISO 1133 (230° C., 2.16 Kg).
  • Propylene homopolymer having a MFR of 6.5 and a fraction soluble in xylene at 25° C. of ⁇ 4 wt %, based upon the weight of the propylene homopolymer.
  • Propylene ethylene copolymer sold under the tradename MOPLEN RP220M being a random propylene ethylene copolymer having an ethylene content of 4 wt %, based upon the weight of the random propylene ethylene copolymer, an MFR of 7, and a fraction soluble in xylene at 25° C. of 7%, based upon the weight of the random propylene ethylene copolymer.
  • Polymers PP1 and PP3 were extruded to form a filament having 1.75 mm of diameter. To extrude PP1, 10 wt % of talc, based upon the total weight of the composition, was added.
  • the printer was a 3D Rostock delta printer.
  • the printer conditions were the followings:
  • the printed sample is shown in FIG. 1 .
  • 5 printer tests were carried out. The print was stopped when one side of the object was detached from the plane, thereby preventing the print of the object. The results are reported in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having: ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %, based upon the weight of the propylene ethylene copolymer; MFR L (Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load) from about 4 to about 20 g/10 min; and xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %, based upon the weight of the propylene ethylene copolymer. The disclosure further provides an extrusion-based additive manufacturing system made from or containing the filament as well as 3D printed articles prepared from the system.

Description

This application is the U.S. National Phase of PCT International Application PCT/EP2017/056495, filed Mar. 20, 2017, claiming benefit of priority to European Patent Application No. 16166589.8, filed Apr. 22, 2016, the contents of which are incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
In general, the present disclosure relates to the field of chemistry. More specifically, the present disclosure relates to polymer chemistry. In particular, the present disclosure relates to a filament made from or containing a propylene ethylene copolymer, for use in an extrusion-based 3D printer.
BACKGROUND OF THE INVENTION
An extrusion-based 3D printer is used to build a 3D model from a digital representation of the 3D model in a layer-by-layer manner by extruding a flowable modeling material. A filament of the modeling material is extruded through an extrusion tip carried by an extrusion head, and is deposited as a sequence of roads on a substrate in an x-y plane. The extruded modeling material fuses to deposited modeling material, and solidifies upon a drop in temperature. The position of the extrusion head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane), and the process is then repeated to form a 3D model resembling the digital representation. Movement of the extrusion head is performed under computer control, in accordance with build data that represents the 3D model. The build data is obtained by slicing the digital representation of the 3D model into multiple horizontally sliced layers. Then, for each sliced layer, the host computer generates a build path for depositing roads of modeling material to form the 3D model.
In the printing process, the filament changes the material of the filament, thereby changing the final mechanical and aesthetic properties of the finished object. In some instances, polylactic acid (PLA) or acrylonitrile, butadiene, styrene (ABS) polymer or polyamides are used for filaments.
It is desirable for the filament to have a constant diameter (in some instances, 1.75 mm or 3 mm); otherwise, finely tuning the amount of material in the printed object is challenging. It is difficult to achieve a constant diameter for the filament, which is believed to depend on the characteristics of the polymer.
It is further desirable that the filament be printable, which, as the term “printable” is used herein, means the filament achieves appropriate adhesion with the plate and among the layers.
SUMMARY OF THE INVENTION
The present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having:
ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %, based upon the weight of the propylene ethylene copolymer;
MFR L (Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load) ranging from about 4 to about 20 g/10 min; and
xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %, based upon the weight of the propylene ethylene copolymer.
BRIEF DESCRIPTION OF THE DRAWINGS
THE FIGURE is a front view of a sample used in print tests. The units of measure are mm. As shown, the printed sample was 5 mm thick.
 DETAILED DESCRIPTION OF THE INVENTION
In a general embodiment, the present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having:
ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %; alternatively from about 3.5 wt % to about 10.0 wt %; alternatively from about 3.8 wt % to about 8.0 wt %, based upon the weight of the propylene ethylene copolymer;
MFR L (Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load) from about 4 to about 20 g/10 min, alternatively from about 5 to about 10 g/10 min; alternatively from about 6 to about 8 g/10 min; and
xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %; alternatively from about 4 wt % to about 25 wt %, based upon the weight of the propylene ethylene copolymer.
As used herein, the term “copolymer” refers to polymer formed from only two monomers: propylene and ethylene.
In some embodiments, the propylene/ethylene copolymer is extruded in a filament having a constant diameter. In some embodiments, the diameter of the filament is about 1.75 mm or about 3 mm. In some embodiments, other diameters are used. In some embodiments, the variation from the nominal diameter is +/−0.05 mm, alternatively +/−0.03 mm. In some embodiments, the diameter of the filament is about 1.75 mm+/−0.05 mm or about 3 mm+/−0.05 mm. In some embodiments, the diameter of the filament is about 1.75 mm+/−0.03 mm or about 3 mm+/−0.03 mm.
It is believed that when amorphous polymeric materials are used, the polymeric materials have little or no ordered arrangements of their polymer chains in their solid states. It is believed that this lack of arrangements reduces the effects of curling and plastic deformation in the resulting 3D model or support structure. In some instances, the amorphous polymeric materials are acrylonitrile-butadiene-styrene (ABS) resins or polycarbonate resins.
While it is believed that crystalline or semicrystalline polymer can exhibit superior mechanical properties than amorphous polymers, it is also believed that crystalline or semicrystalline polymers show undesirable shrinkage effects both when the extruded road is deposited to form a portion of a layer of a 3D model and when the road is cooled. As such, it is further believed that the shrinkage effects renders the crystalline or semicrystalline polymers unsuitable for building 3D objects in an extrusion-based additive manufacturing process.
Contrary to the belief of persons of ordinary skill in the art, the present disclosure provides a semi-crystalline propylene ethylene copolymer suitable for building a 3D model.
Commercially-available examples of the propylene ethylene copolymer include (a) RP220M sold by LyondellBasell, (b) BOREALIS RD204 CF, and (c) LyondellBasell CLYRELL RC 1908.
In some embodiments, the filament is made from or contains additionally additives such as antioxidants, slipping agents, process stabilizers, antiacid and nucleants.
In some embodiments, the filament is made from or contains additionally fillers such as talc, calcium carbonate, wollastonite, glass fibers, glass spheres and carbon derived grades.
In some embodiments, the filament is made from or contains additionally wood powder, metallic powder, marble powder and similar materials.
The following examples are given to illustrate and not to limit the present invention.
EXAMPLES
The data of the propylene polymer materials were obtained according to the following methods:
Xylene-Soluble Fraction at 25° C.
The Xylene Soluble fraction was measured according to ISO 16152, 2005, but with the following deviations (between parentheses).
The solution volume was 250 ml (200 ml).
During the precipitation stage at 25° C. for 30 min, the solution, for the final 10 minutes, was kept under agitation by a magnetic stirrer (30 min, without any stirring at all).
The final drying step was done under vacuum at 70° C. (100° C.).
The content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 grams and then, by difference (complementary to 100), the xylene unsoluble %.
Ethylene (C2) Content
13C NMR of Propylene/Ethylene Copolymers
13C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with cryoprobe, operating at 160.91 MHz in the Fourier transform mode at 120° C.
The peak of the Sββ carbon was used as internal reference at 29.9 ppm. (The nomenclature was according to C. J. Carman, R. A. Harrington and C. E. Wilkes, “Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode,” 10 Macromolecules 536 (1977).) The samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120° C. with a 8% wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
The assignments of the spectra, the evaluation of triad distribution and the composition were made according to Kakugo (M. Kakugo, Y. Naito, K. Mizunuma and T. Miyatake, “Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with δ-titanium trichloride-diethylaluminum chloride” 15 Macromolecules 1150 (1982)) using the following equations:
PPP=100T ββ S PPE=100T βδ S EPE=100T δδ S
PEP=100S ββ S PEE=100S βδ S EEE=100(0.25S γδ+0.5S δδ)/S
S=T ββ +T βδ +T δδ +S ββ +S βδ+0.25S γδ+0.5S δδ
The molar percentage of ethylene content was evaluated using the following equation:
E % mol=100*[PEP+PEE+EEE]
The weight percentage of ethylene content was evaluated using the following equation:
E ⁢ ⁢ % ⁢ ⁢ wt . = 100 * E ⁢ ⁢ % ⁢ ⁢ mol * M ⁢ ⁢ W E E ⁢ ⁢ % ⁢ ⁢ mol * M ⁢ ⁢ W E + P ⁢ ⁢ % ⁢ ⁢ mol * M ⁢ ⁢ W P
where P % mol is the molar percentage of propylene content, while MWE and MWP are the molecular weights of ethylene and propylene, respectively.
The product of reactivity ratio r1r2 was calculated according to Carman (C. J. Carman, R. A. Harrington and C. E. Wilkes, 10 Macromolecules 536 (1977)) as:
r 1 ⁢ r 2 = 1 + ( EEE + PEE PEP + 1 ) ⁢ ( P E + 1 ) ⁢ ( EEE + PEE PEP + 1 ) 0.5
The tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTββ (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm)
Melt Flow Rate (MFR)
The melt flow rate MFR of the polymer was determined according to ISO 1133 (230° C., 2.16 Kg).
The following polymers were used:
PP1
Propylene homopolymer having a MFR of 6.5 and a fraction soluble in xylene at 25° C. of <4 wt %, based upon the weight of the propylene homopolymer.
PP2
A filament of diameter 1.75 mm sold under the tradename PP REPRAP BLACK FILAMENT German RepRap PP Filament 600 g, made from or containing a random propylene ethylene copolymer having an ethylene content of 3 wt %, based upon the weight of the random propylene ethylene copolymer, an MFR of 2 dl/10 min, and a fraction soluble in xylene at 25° C. of 6.2 wt %, based upon the weight of the random propylene ethylene copolymer.
PP3
Propylene ethylene copolymer sold under the tradename MOPLEN RP220M being a random propylene ethylene copolymer having an ethylene content of 4 wt %, based upon the weight of the random propylene ethylene copolymer, an MFR of 7, and a fraction soluble in xylene at 25° C. of 7%, based upon the weight of the random propylene ethylene copolymer.
Polymers PP1 and PP3 were extruded to form a filament having 1.75 mm of diameter. To extrude PP1, 10 wt % of talc, based upon the total weight of the composition, was added.
Print Test
The printer was a 3D Rostock delta printer. The printer conditions were the followings:
Filament diameter mm 1.75 ± 0.03
Nozzle diameter mm 0.4
Temperature first layer ° C. 245
Temperature other layers ° C. 245
1
Layer high mm 0.2
Temperature plate ° C. 100
Support material to vinylic glue
adhere on the plate
Plate material. glass
Infill
100%
printer speed mm/min 3600
Speed first layer  60%
Speed other layers 100%
Speed infill mm/min 4.000
The printed sample is shown in FIG. 1. For each filament, 5 printer tests were carried out. The print was stopped when one side of the object was detached from the plane, thereby preventing the print of the object. The results are reported in Table 1.
TABLE 1
height before detach
(Z) (mm) (average
material measure)
PP1* 0.8
PP2* 1.2
PP3 full (5 mm)
*comparative

Claims (11)

What is claimed is:
1. A process for forming a consumable filament comprising:
forming a filament, wherein the filament comprises:
a propylene ethylene copolymer having:
an ethylene derived units content ranging from 3.0 wt % to 12.0 wt %, based upon the weight of the propylene ethylene copolymer;
a MFR L (Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load) from 4 to 20 g/10 min; and
a xylene solubles content, measured at 25° C., from 3 wt % to 30 wt %, based upon the weight of the propylene ethylene copolymer, and
wherein the filament is formed within an extrusion-based additive manufacturing system.
2. The process according to claim 1, wherein the propylene copolymer has an ethylene derived units content from 3.5 wt % to 10.0 wt %, based upon the weight of the propylene ethylene copolymer.
3. The process according to claim 1, wherein the propylene copolymer has a MFR L from 5 to 10 g/10 min.
4. The process according to claim 1, wherein the propylene copolymer has a xylene solubles content, measured at 25° C., from 4 wt % to 25 wt %, based upon the weight of the propylene ethylene copolymer.
5. The process according to claim 1, wherein the propylene copolymer has an ethylene derived units content from 3.8 wt % to 8.0 wt %, based upon the weight of the propylene ethylene copolymer.
6. The process according to claim 1, wherein the propylene copolymer has a MFR L ranging from 6 to 8 g/10 min.
7. The process according to claim 1, wherein the filament has a constant diameter having a variation of +/−0.05 mm.
8. The process according to claim 1, wherein the filament has a constant diameter having a variation of +/−0.03 mm.
9. The process according to claim 1, wherein the filament has a diameter selected from the group consisting of: (a) 1.75 mm+/−0.05 mm; and (b) 3 mm+/−0.05 mm.
10. The process according to claim 1, wherein the filament has a diameter selected from the group consisting of (a) 1.75 mm+/−0.03 mm; and (b) 3 mm+/−0.03 mm.
11. The process of claim 1 comprising the step of forming a 3D printed article with the filament.
US16/094,647 2016-04-22 2017-03-20 Process for forming a consumable filament Active US10385478B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP16166589 2016-04-22
EP16166589.8 2016-04-22
EP16166589 2016-04-22
PCT/EP2017/056495 WO2017182209A1 (en) 2016-04-22 2017-03-20 Propylene based filament for 3d printer

Publications (2)

Publication Number Publication Date
US20190112732A1 US20190112732A1 (en) 2019-04-18
US10385478B2 true US10385478B2 (en) 2019-08-20

Family

ID=55808987

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/094,647 Active US10385478B2 (en) 2016-04-22 2017-03-20 Process for forming a consumable filament

Country Status (7)

Country Link
US (1) US10385478B2 (en)
EP (1) EP3445793B1 (en)
JP (1) JP6626991B2 (en)
KR (1) KR102009615B1 (en)
CN (1) CN109071723B (en)
BR (1) BR112018070035B1 (en)
WO (1) WO2017182209A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11964437B1 (en) 2021-03-30 2024-04-23 Mark Lamoncha Additive manufacturing by solvent melding of build material

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA202191408A1 (en) * 2018-11-21 2021-08-16 Публичное акционерное общество "СИБУР Холдинг" TRANSPARENT HIGH-FLOW IMPACT-RESISTANT COMPOSITION BASED ON POLYPROPYLENE, METHOD FOR ITS PRODUCTION AND APPLICATION FOR PRODUCTS MANUFACTURED BY 3D PRINTING OR INSURANCE CASTING
US20220402196A1 (en) * 2019-10-01 2022-12-22 Basell Polyolefine Gmbh Propylene based filament for 3d printer
JP7351493B2 (en) * 2019-10-07 2023-09-27 バーゼル・ポリオレフィン・ゲーエムベーハー Polypropylene for extrusion additive manufacturing
KR102412172B1 (en) * 2019-10-30 2022-06-22 롯데케미칼 주식회사 Thermoplastic resin composition and article produced therefrom
KR20240019289A (en) * 2021-06-10 2024-02-14 더블유.알. 그레이스 앤드 캄파니-콘. Polypropylene random copolymer for three-dimensional printing and filaments made therefrom
WO2023004039A1 (en) * 2021-07-22 2023-01-26 Braskem America, Inc. Polypropylene polymers for powder bed fusion based additive manufacturing
DE102022001070A1 (en) 2022-03-29 2023-10-05 Technische Universität Bergakademie Freiberg, Körperschaft des öffentlichen Rechts Thermoplastic binder system and process for the 3D production of ceramic components, metallic components or components based on metal-ceramic composite materials or material composites
WO2025168499A1 (en) 2024-02-07 2025-08-14 Basell Poliolefine Italia S.R.L. Translucent polypropylene-based material for additive manufacturing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161556A (en) 1997-08-12 1999-03-05 Mitsui Chem Inc Monofilament
EP1270628A1 (en) 2001-06-27 2003-01-02 Borealis Technology Oy Propylene random copolymer and process for the production thereof
EP1484345A1 (en) 2003-06-06 2004-12-08 Borealis Technology Oy Process for the production of polypropylene using a Ziegler-Natta catalyst
US20160297103A1 (en) 2013-11-04 2016-10-13 Fine Chemical Co., Ltd. Polymer composition for three-dimensional printer

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4317654A1 (en) * 1993-05-27 1994-12-01 Basf Ag Statistical copolymers of propylene
AU5344999A (en) * 1998-08-31 2000-03-21 Kimberly-Clark Worldwide, Inc. Nonwoven polyolefin fabrics having hydrophilicity
US6943215B2 (en) * 2001-11-06 2005-09-13 Dow Global Technologies Inc. Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
BRPI0508210B1 (en) * 2004-03-19 2016-04-05 Dow Global Technologies Inc fiber, article and extensible nonwoven fabric
WO2007053603A1 (en) * 2005-10-31 2007-05-10 Dow Global Technologies Inc. Propylene-based elastomeric composition
DE102006004672A1 (en) * 2006-01-31 2007-08-02 Basell Polyolefine Gmbh Ethylene/1-olefin copolymer with improved combination of stiffness, environmental stress crack resistance and impact strength is obtained using a specially prepared chromium catalyst
US20120208946A1 (en) * 2009-10-02 2012-08-16 Dow Global Technologies Llc Block copolymers in soft compounds
KR101262308B1 (en) * 2011-01-21 2013-05-08 주식회사 엘지화학 Olefin block copolymer and preparation method thereof
EP2787034A1 (en) * 2013-04-05 2014-10-08 Borealis AG High stiffness polypropylene compositions
CN104230289B (en) * 2014-09-02 2016-08-17 王娟 A kind of 3D prints compositions and its production and use
CN104693637B (en) * 2015-03-04 2017-05-10 珠海天威飞马打印耗材有限公司 Low-melting-point resin material for three-dimensional printer and manufacturing method of low-melting-point resin material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161556A (en) 1997-08-12 1999-03-05 Mitsui Chem Inc Monofilament
EP1270628A1 (en) 2001-06-27 2003-01-02 Borealis Technology Oy Propylene random copolymer and process for the production thereof
EP1484345A1 (en) 2003-06-06 2004-12-08 Borealis Technology Oy Process for the production of polypropylene using a Ziegler-Natta catalyst
US20160297103A1 (en) 2013-11-04 2016-10-13 Fine Chemical Co., Ltd. Polymer composition for three-dimensional printer
JP2016537460A (en) 2013-11-04 2016-12-01 ファインケミカル カンパニー リミテッド Polymer composition for 3D printer

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
International Search Report and Written Opinion dated Apr. 28, 2017 (dated Apr. 28, 2017) for Corresponding PCT/EP2017/056495.
Manfred Kohlen: "Itespresso.de German Reprap Liefert Lebensmittelkonformes3D-Druckmaterial—Itespresso.de", Jan. 16, 2014 (Jan. 16, 2014), XP055258389, Retrieved From the Internet: URL:http://www.itespresso.de/201/01/016/german-reprap-liefert-lebensmittelkonforesm-3d-druckmaterial/?print=1.
O.S. Carneiro et al: "fused Deposition Modeling With Polypropylene", Materials & Design, vol. 83, Oct. 1, 2015 (Oct. 1, 2015), p. 768-776, XP055312954, Amsterdam, NL ISSN: 0264-1275.
O.S. CARNEIRO, A.F. SILVA, R. GOMES: "Fused deposition modeling with polypropylene", MATERIALS & DESIGN, ELSEVIER, AMSTERDAM, NL, vol. 83, 1 October 2015 (2015-10-01), AMSTERDAM, NL, pages 768 - 776, XP055312954, ISSN: 0264-1275, DOI: 10.1016/j.matdes.2015.06.053

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11964437B1 (en) 2021-03-30 2024-04-23 Mark Lamoncha Additive manufacturing by solvent melding of build material

Also Published As

Publication number Publication date
KR20180127500A (en) 2018-11-28
EP3445793A1 (en) 2019-02-27
CN109071723A (en) 2018-12-21
EP3445793B1 (en) 2020-01-01
KR102009615B1 (en) 2019-08-09
WO2017182209A1 (en) 2017-10-26
CN109071723B (en) 2020-12-29
US20190112732A1 (en) 2019-04-18
BR112018070035A2 (en) 2019-02-05
JP2019513913A (en) 2019-05-30
JP6626991B2 (en) 2019-12-25
BR112018070035B1 (en) 2022-08-09

Similar Documents

Publication Publication Date Title
US10385478B2 (en) Process for forming a consumable filament
EP3526376B1 (en) Use of propylene based filament in 3d printing
JP2019513913A5 (en)
US20190127890A1 (en) Propylene terpolymer for filament for 3d printer
JP7351493B2 (en) Polypropylene for extrusion additive manufacturing
JP2019513912A5 (en)
EP4038136B1 (en) Propylene based filament for 3d printer
US20250187260A1 (en) Polypropylene for extrusion additive manufacturing
EP4297972B1 (en) Printing platform for extrusion additive manufacturing

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

AS Assignment

Owner name: BASELL POLIOLEFINE ITALIA, S.R.L., ITALY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DE PALO, ROBERTO;CAVALIERI, CLAUDIO;REEL/FRAME:047274/0793

Effective date: 20180828

STPP Information on status: patent application and granting procedure in general

Free format text: EX PARTE QUAYLE ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO EX PARTE QUAYLE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4