Propylene polymer for 3D printing

Abstract

The propylene copolymer composition comprises a propylene copolymer of 70-95% by weight of propylene and 3.0-25% by weight of at least two α-olefin comonomers. α-olefin comonomers with lower molar masses may be present in amounts of 0.3-10% by weight. The propylene copolymer composition may have a melt flow rate (MFR) in the range of 5.4-250 g / 10 min, a polydispersity index (PI) in the range of 1.0-3.7, and an analytical temperature-controlled elution fractionation full width at half maximum (ATREF FWHM) in the range of 1.0-15.4°C. The method comprises reacting propylene and at least two α-olefin comonomers in one or more vertically stirred gas-phase reactors, and extruding with additives and optionally bis-breaking to produce the propylene copolymer composition.

Description

[Technical Field]

[0001] The embodiments disclosed herein generally relate to propylene copolymer compositions for three-dimensional (3D) printing applications. More specifically, the embodiments disclosed herein relate to a propylene copolymer comprising at least two α-olefin comonomers, and the use of this material for 3D printing applications. [Background technology]

[0002] Additive manufacturing (colloquially known as 3D printing technology) is one of the fastest-growing applications of polymers. Currently, there are four main different methods for additive manufacturing of polymers, including fusion filament manufacturing (FFF), Arburg plastic free forming (APF), stereolithography (SLA), and selective laser sintering (SLS).

[0003] The SLA process requires a liquid plastic resin, a photopolymer, which is then cured by an ultraviolet (UV) laser. SLA machines require excess photopolymer to complete the print, and a common g-code format may be used to translate CAD models into printer assembly instructions. SLA machines typically store excess photopolymer in a tank beneath the print bed, and as the printing process progresses, the bed is lowered into the tank, curing a continuous layer in the process. Due to the small cross-sectional area of ​​the laser, SLA is considered one of the slower additive fabrication methods, as small pieces can take several hours or even days to complete. Furthermore, the limited occupancy and availability of photopolymers result in relatively high material costs.

[0004] The SLS process is similar to SLA, forming parts layer by layer using a high-energy pulsed laser. However, in SLS, the process begins with a tank filled with bulk material in powder form. As printing continues, the bed lowers itself with each new layer, advantageously supporting the overhangs of the upper layers with excess bulk powder not used in forming the lower layers. To facilitate processing, the bulk material is typically heated to just below its transition temperature to allow for faster particle fusion and print movement, as described in US5648450. SLS is not suitable for home or professional desktop applications because it requires large facilities for the safe handling of plastic powder.

[0005] Fusion Filament Manufacturing (FFF) and Arburg Plastic Free Forming (APF) are examples of 3D printing processes using material extrusion. Rather than using lasers to form polymers or sintered particles together, these processes work by extruding and laying continuous layers of material at high temperatures, allowing adjacent layers to cool and bond together before the next layer is deposited. The FFF process typically involves feeding continuous polymer filaments to a print head, melting the polymer, extruding it, and printing to form a part. APF generally refers to the process of feeding polymers in powder, flake, or pellet form to a print head, melting the polymer, extruding it, and printing it in droplets to form a 3D part, as described in EP2739460.

[0006] In the desktop and home 3D printing market, as well as in professional and industrial applications using FFF or APF, PLA (polylactic acid), PETG (polyethylene terephthalate glycol), ABS (acrylonitrile butadiene styrene), PC (polycarbonate), and PA (polyamide) are dominant as printing media.

[0007] Polypropylene, with its low cost and low density (leading to lower weight of printed parts), is a desirable material choice, but current technology does not favor the use of polypropylene. The disadvantages of currently used polypropylene grades compared to PLA, PETG, ABS, PC, and PA are its low tensile modulus, poor adhesion to the print bed, high shrinkage, and significant warping.

[0008] Most 3D printing technologies utilize engineering plastics, which offer superior properties in tensile modulus, print bed adhesion, shrinkage, and warping. Compared to these high-cost engineering plastics, polypropylene generally exhibits slight shortcomings in mechanical properties, but offers advantages in low-temperature printing, density, and molding of odor components (e.g., volatile organic compounds (VOCs)).

[0009] Conventional practices using polypropylene for direct 3D printing involve crosslinked materials that require additional binders besides peroxides, such as the diene CN103980402 or the silane CN103497414. Both patent applications describe the use of polymers for widespread SLS technology, as the crosslinking process is almost always performed after the printing process due to low or even impossible extrusion capacity. The crosslinked polypropylene, existing from an interconnected network exhibiting very poor extrusion, makes filament production, necessary for FFF technology, virtually impossible. The poor extrusion also hinders the use of APF technology.

[0010] GB2515348 discloses a special polypropylene that is flexible at room temperature for producing soft, pliable objects that deform under gravity. Such polymers are undesirable for many applications.

[0011] CN104211876 and CN104031316 focus on complex composite compounds of polypropylene having any of starch, oxysilane, microspheres, and high loadings of toughening agents. This complicates the manufacturing process and increases costs, which is generally undesirable.

[0012] US2012 / 0070619 describes a consumable filament for use in an extrusion-based additive manufacturing system, the consumable filament including a first portion of a first semi-crystalline polymeric material and a second portion of a second semi-crystalline polymeric material, the second semi-crystalline polymeric material having a crystallization temperature higher than the crystallization temperature of the first semi-crystalline polymeric material.

Summary of the Invention

[0013] This summary is to introduce various concepts that will be described in detail in the following "Detailed Description of the Invention". This summary is not intended to identify the important or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0014] In one aspect, the embodiments disclosed herein relate to a propylene copolymer composition, the propylene copolymer composition including a propylene copolymer of propylene in the range of 70 to 95 weight percent (wt%) and at least two α-olefin comonomers in the range of 3.0 to 25 wt%. The at least two α-olefin comonomers can be selected from the group consisting of ethylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. The α-olefin comonomer having a lower molar mass may be included in the range of 0.3 to 10 wt%. The propylene copolymer composition can have a melt flow rate (MFR) in the range of 5.4 to 250 g / 10 min, a polydispersity index (PI) in the range of 1.0 to 3.7, and an analytical temperature rising elution fractionation full width at half maximum (ATREF FWHM) in the range of 1.0 to 15.4 °C.

[0015] In another embodiment, embodiments disclosed herein relate to a method for producing a propylene copolymer composition, comprising reacting propylene with at least two α-olefin comonomers in one or more vertically stirred gas-phase reactors to produce a propylene copolymer. The method may further include extruding the propylene copolymer with additives and optionally bis-breaking to produce the propylene copolymer composition. The resulting propylene copolymer composition may have a melt flow rate (MFR) in the range of 5.4 to 250 g / 10 min, a polydispersity index (PI) in the range of 1.0 to 3.7, and an analytical temperature-induced elution fractionation full width at half maximum (ATREF FWHM) in the range of 1.0 to 15.4 °C.

[0016] Other aspects and advantages of the claimed subject matter will be apparent from the following description and the attached claims. [Brief explanation of the drawing]

[0017] [Figure 1] This embodiment illustrates a fusion filament manufacturing (FFF) system useful for printing articles.

[0018] [Figure 2] An example of a 3D-printed test specimen for determining the tensile modulus of elasticity according to the embodiments of this specification is provided.

[0019] [Figure 3] An example of a 3D-printed test specimen for determining dimensional accuracy according to the embodiments of this specification is provided.

[0020] [Figure 4] An example of a 3D-printed test specimen for determining relative warpage according to the embodiments of this specification is provided.

[0021] [Figure 5] This is a bar graph comparing tensile moduli according to embodiments of this specification.

[0022] [Figure 6] This is a graph comparing ATREF FWHM according to the embodiments of this specification. [Modes for carrying out the invention]

[0023] As mentioned above, fusion filament manufacturing (FFF) and Arburg plastic free forming (APF) are methods of rapid prototyping. This process works by laying continuous layers of material at high temperatures, allowing adjacent layers to cool and bond together before the next layer is deposited.

[0024] Referring to Figure 1, during the fusion filament manufacturing process, the filament 10 may be fed from the spool 11 to the extruder 12. The extruder may use a torque and pinch system 14 to feed and retract the filament as needed. A heater block 16 melts the filament to an appropriate temperature, and the heated filament is extruded out of the heated die 18, laying the extruded material 20 where needed. The print head 8 and / or bed 20 may be moved to the correct xyz positions to position the material as the printing process progresses.

[0025] While a specific type of fusion filament manufacturing process is described and a single spool is illustrated, those skilled in the art will understand that there are many different types of fusion filament manufacturing systems, many of which may include multiple spools and multiple print heads. Similarly, those skilled in the art will understand that Arburg plastic free forming systems, such as those that may use polymer pellets or flakes, can similarly extrude polymers and print them onto three-dimensional objects.

[0026] Embodiments of this specification relate to propylene copolymer compositions and the use of these compositions for FFF and APF 3D printing applications (i.e., embodiments of this disclosure provide 3D print-grade polymers having desirable properties suitable for use in FFF and APF). FFF and APF printing technologies use, in principle, the same printing process, the laying of molten polymer beads / droplets, but differ in how the polymer is supplied to the 3D printer. In FFF technology, a filament pre-extruded from the polymer is introduced into the 3D printer, while APF uses polymer pellets directly derived from the polymer or compounding plant. 3D print propylene copolymer compositions exhibit improved tensile properties and dimensional accuracy compared to existing compositions. These improvements in attributes correspond to propylene copolymer compositions having a higher melt flow rate, a narrower molecular weight distribution, a narrower chemical composition distribution, and higher crystallinity than existing compositions.

[0027] Propylene copolymer composition In one embodiment, the embodiments disclosed herein relate to a propylene copolymer. The propylene copolymer may contain propylene as the majority monomer. In some embodiments, propylene may be present in an amount ranging from 75 to 95 weight percent (wt%). The propylene copolymer may further contain at least two α-olefin comonomers. The at least two α-olefin comonomers may be selected from the group comprising ethylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. In some embodiments, the comonomers include ethylene and 1-butylene. The propylene copolymer may contain a total amount of at least two α-olefin comonomers ranging from 3.0 to 25 weight percent. In other embodiments, the total amount of at least two α-olefin comonomers may be 4.0–22% by weight, 5.2–20% by weight, 6.0–15% by weight, 6.5–14% by weight, 7.0–13% by weight, 7.5–12% by weight, 8.1–11% by weight, 8.5–10.5% by weight, 9.1–10% by weight, or 9.2–9.9% by weight.

[0028] Of at least two α-olefin comonomers, the α-olefin comonomer having the lowest molar mass may be present in the propylene copolymer in an amount of 0.3 to 10% by weight. In one or more embodiments, the α-olefin comonomer with the lowest molar mass may be present in the propylene copolymer in amounts of 0.5 to 8.0% by weight, 1.0 to 6.0% by weight, 1.5 to 5.0% by weight, 1.6 to 4.0% by weight, 1.7 to 3.9% by weight, 1.8 to 3.8% by weight, 1.9 to 3.7% by weight, 2.0 to 3.6% by weight, 2.1 to 3.5% by weight, 2.2 to 3.4% by weight, or 2.3 to 3.3% by weight. In one or more embodiments, the α-olefin comonomer with the lowest molar mass is ethylene.

[0029] Of the at least two α-olefin comonomers, the α-olefin comonomer having the highest molar mass may be present in the propylene copolymer in an amount of 3.0 to 20% by weight, and the total content of the at least two α-olefin comonomers is not greater than the above-mentioned range. In one or more embodiments, the α-olefin comonomer with the highest molar mass may be present in the propylene copolymer in an amount of 3.5 to 18% by weight, 4.0 to 15% by weight, 4.5 to 12% by weight, 5.0 to 10% by weight, or 6.5 to 8.5% by weight, and the total content of the at least two α-olefin comonomers is not greater than the above-mentioned range. In one or more embodiments, the α-olefin comonomer with the highest molar mass is 1-butylene.

[0030] The propylene copolymer compositions according to the embodiments herein may comprise the above-mentioned propylene copolymer and one or more additives. In some embodiments, the additives may be present in amounts ranging from 0.01 to 5% by weight. In other embodiments, one or more additives may be present in amounts ranging from 0.02 to 4% by weight, 0.03 to 3% by weight, 0.04 to 2% by weight, or 0.05 to 1% by weight.

[0031] According to one or more embodiments, one or more additives may be selected from the group consisting of stabilizers, acid scavengers, nucleating agents, antistatic agents, slip agents, antiblocking agents, and combinations thereof.

[0032] According to one or more embodiments, one or more additives may include stabilizers. The stabilizers may include any suitable stabilizers known in the art. Non-limiting examples of stabilizers include phosphites (e.g., BASF IRGAFOS168), phosphonites (e.g., CLARIANT HOSTANOX P-EPQ), sterically interfered phenols (e.g., BASF IRGANOX1010, IRGANOX1076, IRGANOX1330, IRGANOX3114), interfering amines (e.g., BASF TINUVIN622), and thiodipropionates (e.g., BASF IRGANOX PS 802 FL).

[0033] According to one or more embodiments, one or more additives may contain an acid scavenger. The acid scavenger may include any suitable acid scavenger known in the art. The acid scavenger may be selected from the group including metal stearates, hydrotalcite, hydrocalmite, metal oxides, metal carbonates, and combinations thereof. For example, metal stearates may include calcium stearate and zinc stearate. For example, hydrotalcite may include Mg 4.3 Al2(OH) 12.6 It may contain CO3·mH2O(DHT). For example, hydrocalmite may include [Ca2Al(OH)6]OH·mH2O, [Ca2Al(OH)6]CO3·mH2O, [Ca2Al(OH)6]HPO3·mH2O, [Ca2Al(OH)6]SO4·mH2O, [Ca2Al(OH)6]Cl·mH2O, and combinations thereof. For example, metal oxides may include zinc oxide, calcium oxide, magnesium oxide, and combinations thereof. For example, metal carbonates may include zinc carbonate, calcium carbonate, magnesium carbonate, and combinations thereof.

[0034] According to one or more embodiments, one or more additives may include a nucleating agent. The nucleating agent may include any suitable nucleating agent known in the art. For example, the nucleating agent may include talc, sodium benzoate, 1,2,3-tridooxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol, 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol, 1,2-cyclohexanedicarboxylic acid metal salt, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid metal salt, 2,2'-methylene-bis-(4,6-di-te / t-butylphenyl)phosphate metal salt, 2,2'-methylene-bis-(4,6-di-te / t-butylphenyl)benzoate metal salt, or hydroxy-bis(2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate metal salt, and the metal ion can be selected from, for example, lithium, aluminum, sodium, calcium, and magnesium. An example of a commercially available product is Milliken. Examples include HPN-600ei / HPN-68L / HPN-20E / HPN-715 and Adeka NA-11 / NA-21 / NA-71 / NA-27.

[0035] According to one or more embodiments, one or more additives may include an antistatic agent. The antistatic agent may include any suitable antistatic agent known in the art. Examples of antistatic agents include glycerol monostearate (GMS-55, GMS-90) or ethoxylated alkylamines.

[0036] According to one or more embodiments, one or more additives may include a slip agent. The slip agent may include any suitable slip agent known in the art. The slip agent may include erucamide and oleamide.

[0037] According to one or more embodiments, one or more additives may include an antiblocking agent. The antiblocking agent may include any suitable antiblocking agent known in the art. The antiblocking agent may include silica.

[0038] Embodiments of the present disclosure may include 3D-printed articles of propylene copolymer compositions. 3D-printed articles may be printed according to any known method in the art. 3D-printed articles may include articles printed using fusion filament manufacturing (FFF), Arburg plastic free forming (APF), stereolithography (SLA), or selective laser sintering (SLS).

[0039] The propylene copolymer composition may have a melt mass flow rate (MFR). The melt mass flow rate may be determined by a load of 2.16 kg at 230 °C according to the standard method ISO 1133. In one or more embodiments, the propylene copolymer composition may have an MFR in the range of 5.4 to 250 grams per 10 minutes (g / 10 min). In other embodiments, the propylene copolymer composition may have an MFR in the range of 5.5 to 200 g / 10 min, 6.0 to 180 g / 10 min, 7.0 to 150 g / 10 min, 8.0 to 120 g / 10 min, 10 to 100 g / 10 min, 16 to 90 g / 10 min, 21 to 75 g / 10 min, 30 to 60 g / 10 min, or 35 to 43 g / 10 min.

[0040] Propylene copolymer compositions may have a polydispersity index (PI). The PI may correlate with the molecular weight distribution of the propylene copolymer composition. In this specification and the following claims, the PI may be determined as follows. Rheological vibration frequency sweep experiments may be performed on a compression-molded disk using a parallel plate shape with a DHR-2 rheometer (TA Instruments, New Castle, USA) at 210°C, vibration strain amplitude γ0 = 10%, angular frequency ω = 389 to 0.1 rad / sec. Storage modulus G' and loss modulus G'' data are obtained by least-squares polynomial fitting: ln(G') = a² × [ln(G'')] 2 The crossover modulus G can be analyzed by performing +a1 × ln(G'') + a0. C This can be calculated from the fitting parameters as follows: [Number]

[0041] PI can be calculated from the calculated crossover modulus G. C It can be calculated from. [Number]

[0042] In one or more embodiments, the propylene copolymer composition can have a PI in the range of 1.0 to 3.7. In other embodiments, the propylene copolymer composition can have a PI in the ranges of 1.2 to 3.6, 1.5 to 3.4, 1.7 to 3.0, 1.8 to 2.7, or 1.9 to 2.5.

[0043] A measure of the crystallinity of the propylene copolymer composition may include the melting enthalpy (ΔH f ). ΔH f can be determined by the standard method ISO11357-3. In some embodiments, the propylene copolymer composition can have a ΔH f of 61.3 to 150 joules / gram (J / g). In other embodiments, the propylene copolymer composition can have a ΔH f of 61.5 to 140.0 J / g, 61.8 to 120.0 J / g, 62.5 to 100.0 J / g, 63.0 to 90.0 J / g, 65.0 to 80.0 J / g, or 68.0 to 78.0 J / g.

[0044] The width of the chemical composition distribution of a propylene copolymer composition may include ATREF FWHM. ATREF FWHM can be determined by using an automated CRYSTAF-TREF instrument equipped with a heated infrared concentration detector and a composition sensor on which stabilization, crystallization, and elution cycles are performed. Data from the CRYSTAF-TREF instrument can yield an ATREF curve, where the full width at half maximum (FWHM) can be determined. In one or more embodiments, a propylene copolymer composition may have an ATREF FWHM of 1.0 to 15.4°C. In other embodiments, a propylene copolymer composition may have an ATREF FWHM of 2.0 to 14.0°C, 3.0 to 12.0°C, 4.0 to 10.0°C, 5.0 to 9.5°C, 5.5 to 9.0°C, 6.0 to 8.5°C, or 6.5 to 8.0°C.

[0045] 3D Printing Characteristics The tensile properties of a propylene copolymer composition may include the tensile modulus. Tensile tests may be performed using the Z020 (Zwick / Roell, Germany) method, similar to ISO 527, with a preload of 2N, a speed of 1 mm / min for elongation up to 0.25%, and a speed of 50 mm / min for elongation exceeding 0.25%. The tensile modulus may be determined by 3D printing of the test specimen. The test specimen may be conditioned at room temperature and 50% humidity before testing. The test specimen 200 may be printed by material extrusion. In one or more embodiments, the propylene copolymer composition may have a tensile modulus of at least 700 megapascals (MPa). In other embodiments, the propylene copolymer composition may have a tensile modulus of at least 720 MPa, 750 MPa, 780 MPa, or 800 MPa.

[0046] Figure 2 illustrates a test specimen 200 for determining the tensile modulus according to one or more embodiments. The test specimen 200 may be of type 1BA as defined by ISO 527. The test specimen 200 may include a first width 210, which may be 10 mm. The test specimen 200 may include a second width 220, which may be 5 mm. The test specimen 200 may include a first length 230, which may be 75 mm. The test specimen 200 may include a second length 240, which may be 30 mm. The test specimen 200 may include a height 250, which may be 2 mm.

[0047] The propylene copolymer compositions according to the embodiments of this specification have dimensional accuracy. Dimensional accuracy can be determined by 3D printing of a test specimen. A test specimen 300 for determining dimensional accuracy according to one or more embodiments is illustrated in Figure 3. The test specimen 300 may include a first length 310. The test specimen 300 may include a second length 320. The test specimen may include a first width 330. The test specimen may further include a second width 340. The test specimen may include a height 350. The test specimen 300 may be conditioned at room temperature and 50% humidity before testing. The test specimen 300 can be printed by material extrusion, targeting the molding of a structure in which the first length 310 is 5 mm, the second length 320 is 5 mm, the first width 330 is 10 mm, the second width 340 is 10 mm, and the height 350 is 10 mm. Due to the printing process, the laying and cooling of molten polymer layers, the stepwise construction of the structure, and the changes in polymer density during cooling and solidification, the resulting structure may not be exactly the specified dimensions. The difference between the target dimensions and the actual dimensions can be used to provide a measure of the dimensional accuracy of the polymer.

[0048] Dimensional accuracy can be determined from the cumulative deviation. The cumulative deviation can be calculated using the following formula.

number

[0049] Dimensional accuracy can be calculated from the cumulative deviation based on the following formula. Dimensional accuracy [%] = 100% - (Cumulative deviation [%]) / 5

[0050] In one or more embodiments, the propylene copolymer composition may have a dimensional accuracy of at least 88.5% when 3D printed using a die temperature of 190°C. In other embodiments, the propylene copolymer composition may have a dimensional accuracy of at least 89.0%, 89.5%, or 89.9% when 3D printed using a die temperature of 190°C. In one or more embodiments, the propylene copolymer composition may have a dimensional accuracy of at least 96.0% when 3D printed using a die temperature of 240°C. In other embodiments, the propylene copolymer composition may have a dimensional accuracy of at least 96.5%, 97.0%, or 97.3% when 3D printed using a die temperature of 240°C. The propylene copolymer composition may have relative warpage. Relative warpage can be determined by 3D printing of a test specimen. A test specimen 400 for determining relative warpage according to one or more embodiments is illustrated in Figure 4. The test specimen 400 may include a height of 410. The test specimen 400 may include a width of 420. The test specimen 400 may further include a wall thickness of 430. The test specimen 400 may be conditioned at room temperature and 50% humidity before testing. The test specimen 400 can be printed by material extrusion targeting the formation of a structure with a height of 410 = 10 mm, a width of 420 = 10 mm, a wall thickness of 430 = 2 mm, a length of 440 = 80 mm, and a gap height of 460 = 0 mm. Due to the printing process, the laying and cooling of layers of molten polymer, the stepwise construction of the structure, and the changes in polymer density during cooling and solidification, the resulting structure may warp. The difference between the target dimensions and the actual dimensions can be used to provide a measurement of the relative warp of the polymer.

[0051] The relative curvature can be calculated based on the following formula.

number

[0052] Method for preparing a propylene copolymer composition Embodiments of this disclosure may relate to a method for producing a propylene copolymer composition. To produce a propylene copolymer, the method may include reacting propylene with at least two α-olefin comonomers in one or more vertically stirred gas-phase reactors. The method may then include extruding the propylene copolymer with additives and bis-breaking to produce a propylene copolymer composition. The propylene copolymer composition may have an MFR in the range of 5.4 to 250 grams per 10 minutes (g / 10 min). The propylene copolymer composition may have a PI in the range of 1.0 to 3.7. The propylene copolymer composition may have a melting enthalpy (ΔH) of 61.3 to 150 J / g. f The propylene copolymer composition may have an ATREF FWHM of 1.0 to 15.4°C. The propylene copolymer composition may have a tensile modulus of at least 700 MPa. When 3D printed using a die temperature of 190°C, the propylene copolymer composition may have a dimensional accuracy of at least 88.5%. The propylene copolymer composition may further have a relative warpage of 0 to 5%.

[0053] Reacting propylene with at least two α-olefin comonomers in one or more vertically stirred gas-phase reactors may involve the use of any known isospecific catalyst for the polymerization of α-olefins. In one or more embodiments, the catalyst may include an isospecific Ziegler-Natta catalyst. In other embodiments, the catalyst may include an isospecifically supported Ziegler-Natta catalyst containing an internal donor. The support may include SiO2-MgCl2, MgCl2, or MgCl2-nROH. The internal donor may include diisobutyl phthalate (DIBP), 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5), dibutyl succinate (DBS), diethylcyclohexyl succinate (DECS), diethyl-2-ethyl-2-methyl succinate (DEEMS), or 5-tert-butyl-3-methyl-1,2-phenylenedibenzoate (BMPD).

[0054] According to embodiments of the present disclosure, the catalyst may include an isospecific Ziegler-Natta catalyst in the presence of any known silane. The silane may include cyclohexylmethyl-dimethoxysilane, isobutyl(isopropyl)-dimethoxysilane, dicyclopentyl-dimethoxysilane, diisopropyl-dimethoxysilane, diisobutyl-dimethoxysilane, diphenyl-dimethoxysilane, diethylamino-triethoxysilane, and combinations thereof.

[0055] Biscle breaking of propylene copolymers may include any method of biscle breaking known in the art. According to one or more embodiments, biscle breaking may be carried out using a peroxide. The peroxide may include di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, or 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-tripeloxonane.

[0056] Extrusion of propylene copolymers may include any extrusion method known in the art. According to one or more embodiments, the extrusion may be carried out using a twin-screw extruder. The extrusion may include the addition of one or more additives. One or more additives may be selected from the group consisting of stabilizers, acid scavengers, nucleating agents, antistatic agents, slip agents, antiblocking agents, and combinations thereof.

[0057] Embodiments of the present disclosure may include methods for preparing a propylene copolymer composition in which the propylene copolymer composition may have a melt mass flow rate (MFR). The melt mass flow rate may be determined by a load of 230°C and 2.16 kg according to the standard method ISO 1133. In some embodiments, the propylene copolymer composition may have an MFR in the range of 5.4 to 250 grams per 10 minutes (g / 10 min). In other embodiments, the propylene copolymer composition may have an MFR in the range of 5.5 to 200 g / 10 min, 6.0 to 180 g / 10 min, 7.0 to 150 g / 10 min, 8.0 to 120 g / 10 min, 10 to 100 g / 10 min, 16 to 90 g / 10 min, 21 to 75 g / 10 min, 30 to 60 g / 10 min, or 35 to 43 g / 10 min.

[0058] Embodiments of this disclosure may include methods for preparing propylene copolymer compositions in which the propylene copolymer composition may have a polydispersity index (PI). The PI may correlate with the molecular weight distribution of the propylene copolymer composition. In this specification and the following claims, the PI may be determined as follows. Rheological vibration frequency sweep experiments may be performed on a compression-molded disk using a parallel plate shape with a DHR-2 rheometer (TA Instruments, New Castle, USA) at 210°C, vibration strain amplitude γ0 = 10%, angular frequency ω = 389 to 0.1 rad / sec. Storage modulus G' and loss modulus G'' data are obtained by least-squares polynomial fitting: ln(G') = a² × [ln(G'')] 2 The crossover modulus G can be analyzed by performing +a1 × ln(G'') + a0. CThis can be calculated from the fitting parameters as follows:

number

[0059] PI is the calculated crossover modulus G C It can be calculated from this.

number

[0060] In some embodiments, the propylene copolymer composition may have a PI in the range of 1.0 to 3.7. In other embodiments, the propylene copolymer composition may have a PI in the range of 1.2 to 3.6, 1.5 to 3.4, 1.7 to 3.0, 1.8 to 2.7, or 1.9 to 2.5.

[0061] Embodiments of this disclosure describe a propylene copolymer composition with a melting enthalpy (ΔH f The method may include preparing a propylene copolymer composition that may have ΔH. f This can be determined by a standard method, ISO 11357-3, which may include differential scanning calorimetry (DSC). In some embodiments, the propylene copolymer composition has a ΔH of 61.3 to 150 joules / gram (J / g). f In other embodiments, the propylene copolymer composition may have a ΔH of 61.5-140.0 J / g, 61.8-120.0 J / g, 62.5-100.0 J / g, 63.0-90.0 J / g, 65.0-80.0 J / g, or 68.0-78.0 J / g. f It may have.

[0062] Embodiments of the present disclosure may include a method for preparing a propylene copolymer composition in which the propylene copolymer composition may have an analytical temperature-induced elution fractionation full width at half maximum (ATREF FWHM). The ATREF FWHM may be determined using an automated CRYSTAF-TREF instrument equipped with a heated infrared concentration detector and a composition sensor that has undergone stabilization, crystallization, and elution cycling. Data from the CRYSTAF-TREF instrument may yield an ATREF curve in which the full width at half maximum (FWHM) may be determined. The obtained ATREF FWHM may be a measure of the width of the chemical composition distribution of the propylene copolymer composition. In one or more embodiments, the ATREF FWHM may be in the range of 1.0 to 15.4°C. In other embodiments, the ATREF FWHM may be in the range of 2.0 to 14.0°C, 3.0 to 12.0°C, 4.0 to 10.0°C, 5.0 to 9.5°C, 5.5 to 9.0°C, 6.0 to 8.5°C, or 6.5 to 8.0°C.

[0063] Embodiments of this disclosure may include methods for preparing propylene copolymer compositions such that the propylene copolymer composition may have a tensile modulus. Tensile testing may be performed using Z020 (Zwick / Roell, Germany) according to the procedure described in ISO 527, with a preload of 2N, a speed of 1 mm / min for elongation up to 0.25%, and a speed of 50 mm / min for elongation exceeding 0.25%. The tensile modulus may be determined by 3D printing of the test specimen. The test specimen may be conditioned at room temperature and 50% humidity before testing. In some embodiments, the propylene copolymer composition may have a tensile modulus of at least 700 megapascals (MPa). In other embodiments, the propylene copolymer composition may have a tensile modulus of at least 720 MPa, 750 MPa, 780 MPa, or 800 MPa.

[0064] Embodiments of the present disclosure may include methods for producing propylene copolymer compositions that may have dimensional accuracy. Dimensional accuracy can be determined by 3D printing of a test specimen. In some embodiments, a propylene copolymer composition may have at least 88.5% dimensional accuracy when 3D printed using a die temperature of 190°C. In other embodiments, a propylene copolymer composition may have at least 89.0%, 89.5%, or 89.9% dimensional accuracy when 3D printed using a die temperature of 190°C. In some embodiments, a propylene copolymer composition may have at least 96.0% dimensional accuracy when 3D printed using a die temperature of 240°C. In other embodiments, a propylene copolymer composition may have at least 96.5%, 97.0%, or 97.3% dimensional accuracy when 3D printed using a die temperature of 240°C.

[0065] Embodiments of the present disclosure may include methods for preparing propylene copolymer compositions that may have relative warpage. Relative warpage can be determined by 3D printing of a test specimen. In some embodiments, the propylene copolymer composition may have relative warpage of 0-5%. In other embodiments, the propylene copolymer composition may have relative warpage of 0.05-3%, 0.08-2%, and 0.1-1%.

[0066] How to create 3D objects Embodiments of the present disclosure may include a method for producing a 3D article from the above-described propylene copolymer composition. The method may include melting the propylene copolymer composition. The resulting molten composition is then deposited onto a surface using a die. The method further includes forming the 3D article by moving the die and / or the surface relative to each other in xyz space. The 3D article may be formed using a variety of 3D printing systems such as fusion filament manufacturing (FFF), Arburg plastic free forming (APF), and selective laser sintering (SLS).

[0067] The propylene copolymer composition may be in the form of a filament, pellet, or flake suitable for each printing system. The filament, pellet, or flake may be supplied to an extruder which may include a heater block. The energy provided by the heater block and extruder can melt the propylene copolymer composition and increase its temperature above its melting point. The energy provided can also be used to increase the temperature of the polymer melt to a desired extrusion temperature, i.e., the temperature at which the polymer melt is pushed through the die of the print head and deposited on the print surface. Useful die temperatures for the propylene copolymer compositions herein may include, for example, temperatures in the range of about 150°C to 280°C.

[0068] Next, the molten composition is deposited onto the surface using a die. The melting and deposition of the molten composition can be carried out, for example, using a single-screw extruder equipped with a melting pump and a die. The die may have a diameter of 0.04 to 2 mm. After depositing the polymer on the surface, the propylene copolymer composition may be cooled and solidified to provide the final printed product.

[0069] According to one or more embodiments, the surface may include a print bed. In some embodiments, the print bed may be heated and operated at a temperature ranging from room temperature to a maximum temperature of about 150°C. The print bed temperature must be lower than the melting temperature of the propylene copolymer composition, thus providing cooling of the molten material and solidification into the desired 3D object. In some embodiments, the print bed may have print dimensions (x, y, z) of 300 mm × 200 mm × 260 mm, although larger or smaller print beds may be used. The print bed may be made from, for example, PEI.

[0070] Embodiments of the present disclosure may include forming a 3D article by moving dies and / or surfaces relative to each other in xyz space and depositing a propylene copolymer composition. Moving may include positioning the propylene copolymer extruded body at the correct xyz positions required for forming the 3D article. The shape of the deposited propylene copolymer composition may include droplets, strands, rods, or discs. The propylene copolymer composition may be deposited in a pattern to form layers. Forming the 3D article may include depositing multiple layers of the propylene copolymer composition.

[0071] As described above, 3D printing of polymers presents challenges related to changes in shape and dimensions during the cooling and solidification of the polymer after extrusion and deposition onto the print surface. However, propylene copolymer compositions according to the embodiments herein have been found to overcome some or all of these challenges, as detailed in the following examples.

[0072] Embodiments of the present disclosure may offer at least one of the following advantages: Propylene copolymer compositions may offer higher dimensional accuracy and higher tensile modulus with similar low relative warpage compared to state-of-the-art compositions. Improvements in these attributes may result in higher melt flow rates, narrower molecular weight distribution (PI), narrower chemical composition distribution (ATREF FWHM), and higher crystallinity (ΔH) than state-of-the-art compositions. f This may be due to the use of a composition of a copolymer of propylene and at least two α-olefin comonomers, and additives, having the following properties: Compositions with lower average molecular weight (higher melt flow rate) cannot be expected to exhibit superior processing behavior, as seen in compositions with lower relative warpage and higher dimensional accuracy. The prior art teaches that low-crystallinity materials may exhibit better processing behavior, such as less relative warpage and higher dimensional accuracy. Therefore, it cannot be expected or predicted that higher-crystallinity materials will exhibit superior processing behavior.

[0073] Prior art has not addressed the influence of the breadth of molecular weight distribution (PI) and chemical composition distribution (ATREF FWHM) on the properties of 3D printed articles. In other applications, such as heat seal layers, a broad molecular weight distribution (PI) and a broad chemical composition distribution (ATREF FWHM) are known to be advantageous. Embodiments of this disclosure report PI values ​​as evidence of a narrower molecular weight distribution. Embodiments of this disclosure also report ATREF FWHM values ​​as evidence of a narrower chemical composition distribution. The compositions described herein may be advantageous for 3D printing because the reported PI and ATREF FWHM values ​​correlate with 3D printed articles having low relative warpage and high dimensional accuracy.

[0074] Embodiments of this disclosure may be particularly useful for 3D printing by material extrusion and may be used in the form of pellets, powders, or filaments. The compositions described herein can be successfully printed at temperatures below 200°C, thereby enabling use on a wide range of consumer 3D printers with low maximum printhead temperatures. [Examples]

[0075] Table 1 summarizes the material parameters of all comparative examples and examples of the present invention. Comparative Example CE1 is a commercially available copolymer of propylene, ethylene, and 1-butylene (Adsyl 5C30F, LyondellBasell, USA). Comparative Example CE2 is a 3D printing filament based on a copolymer of propylene, ethylene, and 1-butylene (Innofil3D PP Natural, d=1.75mm, BASF3D Printing Solutions, Germany). CE3 is a 3D printing filament based on a copolymer of propylene and ethylene (PP Transparent, d=1.75mm, Verbatim Europe, Germany). Example IE of the present invention is an isospecific SiO2 containing diisobutyl phthalate (DIBP) as an internal donor. 2-The copolymer of propylene, ethylene, and 1-butylene was prepared by synthesizing it in a single vertically stirred gas-phase reactor (Novolen type) at 26 bergs and 75°C using a MgCl2-supported Ziegler-Natta catalyst. An external donor (cyclohexylmethyl-dimethoxysilane) was supplied to the reactor to control the incorporation of comonomers and increase the isospecificity of the catalyst. Hydrogen was supplied to the reactor to control the polymer molecular weight, and the supply rate was adjusted to achieve an MFR of approximately 1 g / 10 min (ISO1133, 230°C, 2.16 kg). The resulting powder was extruded on a twin-screw extruder with 650 ppm Irganox 1010 (BASF SE, Germany), 1350 ppm Irgafos 168 (BASF SE, Germany), and 500 ppm DHT-4A (Kisuma Chemicals BV, Netherlands) for the total composition. During extrusion, the polymer was screw-breaked using peroxide, achieving an MFR of approximately 43 g / 10 min (ISO1133, 230°C, 2.16 kg).

[0076] The melt flow rate (MFR) was determined according to ISO 1133 at 230°C and a load of 2.16 kg. Peak melting temperature T pm and enthalpy of melting ΔH f The determination was made according to ISO 11357-3. The heating and cooling protocols were as follows: [1] 0°C to 200°C at +20K / min, [2] 200°C for 5 minutes, [3] 200°C to 0°C at -20K / min, [4] 0°C for 5 minutes, [5] 0°C to 200°C at +20K / min. Peak melting temperature T pm and enthalpy of melting ΔH fThe second heating cycle (step [5]) was evaluated. "Ethylene content" (C2) refers to the weight percentage of -CH2-CH2- units in the polymer derived from ethylene polymerization. "Butylene content" (C4) refers to the weight percentage of -CH2-C3H6- units in the polymer derived from 1-butylene polymerization. Total comonomer content refers to the sum of all comonomer content in weight percentage. Ethylene content (C2) and butylene content (C4) were determined by Fourier transform infrared spectroscopy (FTIR) on a 200 ± 50 μm film using a Tensor 27 FTIR spectrometer (Bruker Corp., USA). Films were prepared using a hot press at 200°C and 50 bar, and spectral absorption was corrected for the actual film thickness. FTIR spectra were obtained at 4000–400 cm⁻¹. -1 Acquired in the mid-infrared region, 900-600 cm -1 The band is 13 The spectra were evaluated using a partial least squares (PLS) algorithm, compared to the spectra of a reference sample calibrated by 13C NMR (Haaland et al. Anal. Chem. 1988, 60, 1193-1202). Rheological vibration frequency sweep experiments were performed on a compression-molded disk using a parallel plate shape with a DHR-2 rheometer (TA Instruments, New Castle, USA) at 210°C, vibration strain amplitude γ0 = 10%, angular frequency ω = 389 ~ 0.1 rad / sec. Storage modulus G' and loss modulus G'' data were fitted using least squares polynomial fitting: ln(G') = a² × [ln(G'')]. 2 The analysis was performed by implementing +a1 × ln(G'') + a0. Crossover modulus G C This was calculated from the fitting parameters as follows:

number

[0077] Several rheological parameters were calculated as measures of the width of the molecular weight distribution. PI is the dispersion exponent M. w / M nIn this configuration, PDR provides a measure of shear thinning intensity, and ER relates to the width of the high molecular weight side of the molecular weight distribution.

number

number

number

[0078] To determine the width of the chemical composition distribution, analytical temperature-induced elution fractionation (ATREF) was performed using an automated CRYSTAF-TREF instrument (PolymerChar SA, Spain) equipped with a heated infrared (IR) concentration detector with a composition sensor and a capillary viscometer detector. Polymer solutions were prepared at a concentration of 3 ± 0.25 mg / mL in 1,2-dichlorobenzene (stabilized with 500 ppm of 2,6-di-tert-butyl-4-methylphenol) at 150°C for 90 minutes. After dissolution was complete, the sample was transferred to an ATREF column where stabilization, crystallization, and elution cycles were performed. During stabilization, the column was cooled from 150°C to 95°C at -40°C / min and then held at 95°C for 45 minutes. The crystallization step was performed by cooling from 95°C to 35°C at a cooling rate of -0.5°C / min. At the end of the crystallization step, the column was held at 35°C for 10 minutes. Subsequently, the column contents were eluted for 10 minutes, and the soluble fraction was recovered. The elution step was performed by heating from 35 to 140°C at a heating rate of +1°C / min while maintaining a constant solvent flow rate of 0.5 mL / min. The obtained ATREF data in the 35–140°C range (excluding the soluble fraction) were divided by their respective maximum signal intensities to obtain rescaled data. As a measure of the width of the chemical composition distribution, the full width at half maximum (FWHM) was determined by calculating the temperature difference between two points on the ATREF curve where the rescaled signal intensity was 0.5 in each case.

[0079] Table 1: Analytical parameters of different propylene polymer compositions. (*) Comparative examples. (†) Examples of the invention. [Table 1]

[0080] The Arburg Plastic Freeforming (APF) 3D printing test was performed using a Freeformer 200-3X 3D printer (Arburg GmbH + Co KG, Germany) with a maximum build volume temperature of 120°C, a maximum processing temperature of 350°C, and a maximum print dimensions (x, y, z) of 189 mm × 134 mm × 230 mm. Arburg Freeformer technology is based on a high-frequency nozzle closure that ejects droplets of molten polymer onto a moving partial carrier. The test process parameters are summarized in Table 2. Process conditions (temperature, throughput, etc.) were optimized to achieve the best print performance recommended by the equipment supplier for new material certification.

[0081] Table 2: Processing parameters for Arburg plastic free forming (APF) 3D printing tests using selected examples and comparative examples of the present invention from Table 1. (*) Comparative example. (†) Example of the invention. [Table 2]

[0082] The embodiment IE of the present invention shown in Table 1 was extruded into a filament with d=1.75±0.05mm using an FT-E20 single-screw extruder (Collin Lab Solution&Pilot GmbH, Germany) equipped with a melt pump and a 2mm die. The extruded strand was cooled using a water bath at room temperature and then dried using air. Material diameter was monitored using a Sikora 2050T gauge head (Sikora, Germany) and collected using a take-up / wind-up system (Collin Lab Solution&Pilot GmbH, Germany). Fusion filament manufacturing (FFF) 3D printing tests were performed on a Triple F Mini 3D printer (SKZ KFE gGmbH, Germany) with a maximum print bed temperature of 150°C, a maximum processing temperature of 395°C, and a maximum print dimensions (x, y, z) of 300mm × 200mm × 260mm. The process parameters of the tests are summarized in Table 3.

[0083] Table 3: Processing parameters for fusion filament manufacturing (FFF) 3D printing tests using selected examples and comparative examples of the present invention from Table 1. (*) Comparative example. (†) Example of the invention. [Table 3]

[0084] Test sample Different test specimens were printed to determine the performance of the selected comparative examples and embodiments of the present invention in Table 1 in 3D printing by material extrusion. Figure 3 shows the test specimens used to quantify dimensional accuracy. The cumulative deviation from the desired dimensions was determined based on Equation 5, and dimensional accuracy was calculated using Equation 6.

number

[0085] The degree of warpage (Figure 4) was quantified, and test samples used to determine the mechanical properties (Figure 2) of 3D-printed specimens from selected examples and comparative examples of the present invention in Table 1 are shown. Absolute warpage is the gap height h in the z direction between the printed specimen (inverted) and the construction platform. warp It was determined by measuring the relative curvature, l warp This was calculated based on Equation 7, where is the actual length of the sample in the x-direction (longest dimension). Relative curvature [%] = h warp [mm] / l warp [mm] × 100% (7)

[0086] The mechanical properties of the selected examples and comparative examples of the present invention in Table 1 were determined by analyzing 3D-printed test specimens of type 1BA as defined by ISO 527 (Figure 2). Tensile tests were performed using Z020 (Zwick / Roell, Germany), similar to ISO 527, with a preload of 2N, a speed of 1 mm / min for elongation up to 0.25%, and a speed of 50 mm / min for elongation exceeding 0.25%. All test specimens were conditioned at room temperature and 50% humidity prior to testing.

[0087] Tables 4 and 5 summarize the test results for tensile strength, dimensional accuracy, and relative warpage for the selected examples and comparative examples of the present invention in Table 1. Example IE1 of the present invention exhibits the highest tensile modulus E compared to state-of-the-art compositions. t This demonstrates that the composition of the present invention can be used in applications requiring high rigidity (e.g., automotive / aerospace). Surprisingly, using Example IE1 of the present invention results in a higher enthalpy of melting ΔH compared to using state-of-the-art compositions. f As characterized by, higher dimensional accuracy was achieved despite higher MFR (lower average molecular weight) and higher crystallinity. This is particularly beneficial for complex and functional parts where high dimensional accuracy is required. High enthalpy of melting ΔH f Despite the high crystallinity characterized by the above, the sample based on Example IE1 of the present invention exhibited similar relative warpage to that of state-of-the-art compositions. This was unexpected, as the prior art teaches that warpage correlates with the degree of crystallinity.

[0088] Table 4: Tensile test results, dimensional accuracy results, and warpage results from Arburg plastic freeforming (APF) 3D printing tests in selected examples and comparative examples of the present invention from Table 1. (*) Comparative example. (†) Example of the invention. [Table 4]

[0089] Table 5: Tensile test results, dimensional accuracy results, and warpage results from fusion filament fabrication (FFF) 3D printing tests in selected examples and comparative examples of the present invention from Table 1. (*) Comparative example. (†) Example of the invention. [Table 5]

[0090] Figure 5 is a bar graph comparing the tensile modulus of Example (IE1) of the present invention with that of Comparative Examples (CE1, CE2, CE3).

[0091] Figure 6 is a graph comparing the ATREF FWHM of Example (IE1) of the present invention with that of comparative examples (CE1, CE2, CE3).

[0092] Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily understand that many modifications are possible in the exemplary embodiments without substantially departing from the present invention. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims.

Claims

1. A propylene copolymer composition, It contains a propylene copolymer, and the propylene copolymer is Propylene in the range of 70-95% by weight, As determined by Fourier transform infrared (FTIR) spectroscopy, it comprises at least two α-olefin comonomers in the range of 3.0 to 25% by weight, The at least two α-olefin comonomers are selected from the group consisting of ethylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. The comonomer having a lower molar mass is in the range of 0.3 to 10% by weight, as determined by FTIR. The propylene copolymer composition, when determined according to ISO 1133 at 230°C and a load of 2.16 kg, has a melt flow rate (MFR) in the range of 5.4 to 250 g / 10 min, and when determined by a rheological vibration frequency sweep at 210°C, has a PI in the range of 1.0 to 3.7, with PI = 10. ５ Pa / G ｃ and G ｃ A composition having a polydispersity index (PI) of 1,2-dichlorobenzene, where =G'=G'' (crossover modulus), 1) cooling from 150 to 95°C at -40°C / min, 2) maintaining 95°C for 45 minutes, 3) cooling from 95°C to 35°C at -0.5°C / min, 4) maintaining 35°C for 10 minutes, and 5) heating from 35 to 140°C at +1°C / min, and having an analytical heating elution fractional full width at half maximum (ATREF FWHM) in the range of 1.0 to 15.4°C, as determined by CRYSTAF-TREF in 1,2-dichlorobenzene.

2. The composition according to claim 1, wherein the at least two α-olefin comonomers are ethylene and 1-butylene.

3. The composition according to claim 1 or 2, further comprising 0.01 to 5% by weight of one or more additives selected from the group consisting of stabilizers, acid scavengers, nucleating agents, antistatic agents, slip agents, antiblocking agents, and combinations thereof.

4. The propylene copolymer composition, when determined by differential scanning calorimetry according to ISO 11357-3, has a melting enthalpy ΔH of 61.3 to 150 J / g. ｆ A composition according to any one of claims 1 to 3, having the following characteristics.

5. The propylene copolymer composition according to any one of claims 1 to 4, wherein the propylene copolymer composition has a tensile modulus of at least 700 MPa as determined by a tensile test of a 3D-printed test specimen similar to ISO 527.

6. A three-dimensionally printed article comprising the composition according to any one of claims 1 to 5.

7. A method for preparing a propylene copolymer composition, To produce a propylene copolymer, propylene is reacted with at least two α-olefin comonomers in one or more vertically stirred gas-phase reactors. To produce a propylene copolymer composition, the propylene copolymer is extruded together with additives and optionally subjected to screw breaking. The propylene copolymer composition, when determined according to ISO 1133 at 230°C and a load of 2.16 kg, has a melt flow rate (MFR) in the range of 5.4 to 250 g / 10 min, and when determined by a rheological vibration frequency sweep at 210°C, has a PI in the range of 1.0 to 3.7, with PI = 10. ５ Pa / G ｃ and G ｃ A method for 1,2-dichlorobenzene having a polydispersity index (PI) of 1.0 to 15.4°C, determined by CRYSTAF-TREF, where =G'=G'' (crossover modulus of elasticity), 1) cooling from 150 to 95°C at -40°C / min, 2) maintaining 95°C for 45 minutes, 3) cooling from 95°C to 35°C at -0.5°C / min, 4) maintaining 35°C for 10 minutes, and 5) heating from 35 to 140°C at +1°C / min, and evaluating the full width at half maximum (FWHM) of the peak between 35 and 140°C.

8. The method according to claim 7, wherein the propylene is reacted with at least two α-olefin comonomers, the reaction being carried out with a Ziegler-Natta catalyst, an internal donor, and an external donor.

9. The method according to claim 8, wherein the Ziegler-Natta catalyst comprises an isospecifically supported Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as an internal donor.

10. The method according to claim 8, wherein the external donor comprises a silane selected from the group consisting of cyclohexylmethyl-dimethoxysilane, isobutyl(isopropyl)-dimethoxysilane, dicyclopentyl-dimethoxysilane, diisopropyl-dimethoxysilane, diisobutyl-dimethoxysilane, diphenyl-dimethoxysilane, diethylamino-triethoxysilane, and combinations thereof.

11. The method according to any one of claims 7 to 10, wherein extruding the propylene copolymer composition and optionally screw-breaking it comprises screw-breaking it with a peroxide.

12. The propylene copolymer composition, when determined by differential scanning calorimetry according to ISO 11357-3, has a melting enthalpy ΔH of 61.3 to 150 J / g. ｆ The method according to any one of claims 7 to 11, comprising:

13. The method according to any one of claims 7 to 12, wherein the propylene copolymer composition has a tensile modulus of at least 700 MPa as determined by a tensile test of a 3D-printed test specimen similar to ISO 527.

14. A method for manufacturing a three-dimensional article, To form the molten composition, the composition according to any one of claims 1 to 5 is melted, Depositing the molten composition onto the surface using a die, A three-dimensional article is formed by moving the die and / or the surface relative to each other in xyz space. Methods that include...

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