ADDITIVE MANUFACTURING METHOD FOR MAKING A THREE-DIMENSIONAL OBJECT

Abstract

The present disclosure relates to an additive manufacturing (AM) method for making a three-dimensional (3D) object, using a part material (M) comprising at least one poly(ether ketone ketone) (PEKK) polymer, in particular to a 3D object obtainable by Fused Deposition Modelling (FDM) or Fused Filament Fabrication (FFF) from this part material (M).

Claims

1-15. (canceled)

16. An additive manufacturing (AM) method for making a three-dimensional (3D) object, comprising extruding a part material (M) comprising a polymer component comprising: from 55 to 99 wt. % of at least one poly(ether ketone ketone) (PEKK) polymer, and from 1 to 45 wt. % of at least one poly(ether imide) (PEI) polymer, based on the total weight of the polymer component.

17. The method of claim 16, wherein the PEKK comprises at least one recurring unit (R.sup.M) and at least one recurring unit (R.sup.P), wherein recurring unit (R.sup.M) is represented by formula (I): ##STR00017## each R.sup.1 and R.sup.2, at each instance, is independently selected from the group consisting of an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium; and each i and j, at each instance, is an independently selected integers ranging from 0 to 4.

18. The method of claim 17, wherein the PEKK consists essentially in recurring units (R.sup.P) and (R.sup.M).

19. The method of claim 17, wherein the PEKK has a ratio of recurring units (R.sup.P)/(R.sup.M) ranging from 65/35 to 95/5.

20. The method of claim 16, wherein the part material (M) further comprises

0. 1 wt. % to 60 wt. %, with respect to the total weight of the part material, of an additive selected from the group consisting of flow agents, fillers, colorants, lubricants, plasticizers, stabilizers, flame retardants, nucleating agents and combinations thereof.

21. The method of claim 16, wherein the PEI is a poly(ether imide) (PEI) polymer comprising recurring units (R.sub.PEI) of formulas (XXIV) or (XXV), in imide forms, or their corresponding amic acid forms and mixtures thereof: ##STR00018##

22. The method of claim 16, wherein the part material (M) is the shape of a filament having a cylindrical or ribbon-like geometry, its diameter or at least one its section having a size varying between 0.5 mm and 5 mm.

23. The method of claim 16, wherein the part material (M) is the form of pellets having a size ranging from 1 mm to 1 cm.

24. The method of claim 16, wherein the part material (M) comprises a polymer component comprising: from 77 to 99 wt. % of at least one poly(ether ketone ketone) (PEKK) polymer, and from 1 to 23 wt. % of at least one poly(ether imide) (PEI) polymer, based on the total weight of the polymer component.

25. The method of claim 16, wherein the part material (M) comprises a polymer component comprising: from 85 to 99 wt. % of at least one poly(ether ketone ketone) (PEKK) polymer, and from 1 to 15 wt. % of at least one poly(ether imide) (PEI) polymer, based on the total weight of the polymer component.

26. A filament material having a cylindrical geometry and a diameter comprised between 0.5 and 5 mm ±0.15 mm, comprising a polymer component comprising: from 50 to 99 wt. % of at least one poly(ether ketone ketone) (PEKK) polymer, and from 1 to 45 wt. % of at least one poly(ether imide) (PEI) polymer, based on the total weight of the polymer component.

27. The filament material of claim 26, wherein the filament is obtained by a melt-mixing process carried out by heating the polymer component above its melting temperature and melt-mixing the components of the part material.

28. The filament material of claim 26, wherein the polymer component comprises at least 80 wt. % of the blend of PEKK and PEI polymers, based on the total weight of polymeric component of the filament.

29. A three-dimensional (3D) object obtainable by an extrusion-based 3D printing process, from a part material (M) comprising a polymer component comprising: from 55 to 99 wt. % of at least one poly(ether ketone ketone) (PEKK) polymer, and from 1 to 45 wt. % of at least one poly(ether imide) (PEI) polymer, based on the total weight of the polymer component.

30. A method of manufacturing a 3D object, the method comprising using of a part material (M) comprising a polymer component comprising: from 55 to 99 wt. % of at least one poly(ether ketone ketone) (PEKK) polymer, and from 1 to 45 wt. % of at least one poly(ether imide) (PEI) polymer, based on the total weight of the polymer component in the part material (M), in extrusion-based 3D printing to manufacture a 3D object.

Description

EXAMPLES

[0173] The disclosure will be now described in more detail with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the disclosure.

[0174] Starting Materials

[0175] PEKK: PEKK 71/29 was prepared according to the following method:

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 112.50 g of diphenyl sulfone (DPS), 23.054 g of 1,3-BHBB, 16.695 g of 1,4-BHBB and 41.172 g of 1,4-DFDK. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O.sub.2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min). The reaction mixture was heated slowly to 270° C. At 270° C., 13.725 g of Na.sub.2CO.sub.3 and 0.078 g of K.sub.2CO.sub.3 was added via a powder dispenser to the reaction mixture over 60 minutes. At the end of the addition, the reaction mixture was heated to 310° C. at 1° C./minute. After 2 minutes at 310° C., 1.207 g of 1,4-DFDK were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 0.741 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 0.402 g of 1,4-DFDK were added to the reactor and the reaction mixture was kept at temperature for 15 minutes. Another charge of 15 g of diphenyl sulfone was added to the reaction mixture, which was kept under agitation for 15 minutes.
The reactor content was then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12. 0.67 g of NaH.sub.2PO.sub.4.2H.sub.2O and 0.62 g of Na.sub.2HPO.sub.4 were dissolved in 1200 mL DI water for the last wash. The powder was then removed from the reactor and dried at 120° C. under vacuum for 12 hours yielding 72 g of a yellow powder.
PPSU: Rader) PPSU R-5800 NT, available from Solvay Specialty Polymers USA L.L.C.
PEI: Ultem® PEI 1000, available from Sabic Innovative Plastics
PEEK: KetaSpire® PEEK KT-880 MF, available from Solvay Specialty Polymers USA L.L.C.
PSU—polysulfone: Udel® PSU P-1850P, available from Solvay Specialty Polymers USA L.L.C.
PES—poly(ether sulfone): Veradel® PES A-301 NT, available from Solvay Specialty Polymers USA L.L.C.
TPI: Aurum® PL450C, available from Mitsui Chemicals

Example 1

[0176] Preparation of Formulations

[0177] All polymer blends were prepared by first tumbling the polymers to be compounded, in resinous form, for about 20 minutes. Then, each formulation was melt compounded using a 26 mm diameter Coperion® ZSK-26 co-rotating partially intermeshing twin screw extruder having an L/D ratio of 48:1. The barrel sections 2 through 12 and the die were heated to set point temperatures as follows: Barrels 2-6: 360° C., Barrels 7-12: 350° C., Die: 350° C. In each case, the resin blends were fed at barrel section 1 using a gravimetric feeder at throughput rates in the range 35-40 lb/hr. The extruder was operated at screw speeds of around 200 RPM. Vacuum was applied at barrel zone 10 with a vacuum level of about 27 inches of mercury. A single-hole die was used for all the compounds to give a filament approximately 2.4 to 2.5 mm in diameter and the polymer filament exiting the die was cooled in water and fed to the pelletizer to generate pellets approximately 2.0 mm in length. Pellets were annealed prior being injection molded, as follows: 2 h @ 175° C. followed by 2 h @ 200° C.

[0178] Test Methods

[0179] DSC (Tg, Tc, Heat of Fusion)

[0180] Tg is determined on the 2.sup.nd heat scan in differential scanning calorimeter (DSC) according to ASTM D3418, using a heating and cooling rate of 20° C./min.

[0181] Tc is determined on the 1St cool scan in differential scanning calorimeter (DSC) according to ASTM D3418, using a heating and cooling rate of 20° C./min.

[0182] Heat of fusion is determined on the 2.sup.nd heat scan in differential scanning calorimeter (DSC) according to ASTM D3418, using a heating rate of 20° C./min.

[0183] Double-Gated Injection Molding

[0184] ASTM tensile bars with and without weld lines were injection molded on a Toyo Si-110-6 F200HD injection molding machine at a mold temperature of 225° C., resulting in the formation of opaque tensile specimens, which were subsequently subject to tensile testing. To ascertain the weld line strength of these blends the weld-line strengths were measured against the base case (single-gated) with no weld line.

[0185] Tensile Strength

[0186] Tensile strength and modulus were determined according to the ASTM D638 method with ASTM Type I bars.

[0187] Transparency/Haze

[0188] Flat plastic chips were molded using a Mini-Jector with front zone 377° C. (710° F.), rear zone 377° C. (710° F.), nozzle temp 382° C. (720° F.), mold temp 93° C. (200° F.), cycle time 21 s, inject time 10 s, and pressure of 39 atm (570 psi). ASTM D-1003 provides a measuring method for haze. Haze is the ratio of diffused light transmittance to the total light transmittance expressed as a percent.

[0189] The components and their respective amounts in the test bars (according to the present disclosure or comparative) and the mechanical properties of the same are reported in Tables 1-3 below (5 test bars/mean value).

[0190] Results

TABLE-US-00001 TABLE 1 1 2 3 4 C: comparative C C I C I: according to the disclosure PEKK 100 83 83 83 PPSU 17 PEI 17 PEEK 17 Tg, 2.sup.nd heat (° C.) 164 170 176 163 Tc, 1.sup.st cool (° C.) 275 253 258 269 Heat fusion, 2.sup.nd heat (J/g) 48 33 36 46 Modulus of Elasticity (GPa) 4.2 ± 0  3.9 ± 0.2 3.9 ± 0 4.3 ± 0.1 Tensile strength (MPa) 95.8 ± 7.2 93.8 ± 12.3  108.2 ± 12.1 117.9 ± 2.2  Nominal Tensile Strain at Break (%)  2.9 ± 0.3 3.4 ± 0.6 4.6 ± 1 5.4 ± 3.5 Haze 47.49 11.22 8.71 44.62

TABLE-US-00002 TABLE 2 5 6 7 C: comparative C C C I: according to the disclosure PEKK 83 83 83 PSU 17 PES 17 TPI 17 Tg, 2.sup.nd heat (° C.) 166 166 167 Tc, 1.sup.st cool (° C.) 276 274 282 Heat fusion, 2.sup.nd heat (J/g) 37 38 37 Modulus of Elasticity (GPa) 3.8 ± 0   4 ± 0 4.2 ± 0.2 Tensile strength (MPa) 47.8 ± 4   50.3 ± 5   91.7 ± 9.5  Nominal Tensile Strain at Break (%) 1.4 ± 0.1 1.4 ± 0.1 3.1 ± 0.5 Haze not not 8.02 measured measured (fully (fully opaque) opaque)

[0191] The inventive blend of PEKK and PEI (Ex3) provides a good set of properties, that-is-to say a good compromise of both mechanical and optical properties, in comparison with other PEKK/amorphous resins.

Example 2

[0192] The formulations 8-12 of example 2 were prepared according to the method described in example 1 and the same test methods were applied to the formulations, except that these formulations were melt compounded with a different process, described as follows: The formulations were melt compounded using an 18 mm Leistritz co-rotating intermeshing twin screw extruder. The extruder had 6 barrel zones with the following set points: barrels 2 through 5 being heated (corresponding to zones 1 through 4): 360° C.; Barrel 6: 350° C.; Adapter: 350° C.; Die: 350° C. In each case, the resin blends were fed at barrel section 1 using a gravimetric feeder at throughput rates in the range 15-17 lb/hr. The extruder was operated at screw speeds of around 125 RPM. A single-hole die was used for all the compounds to give a filament approximately 2.4 to 2.5 mm in diameter and the polymer filament exiting the die was cooled in water and fed to the pelletizer to generate pellets approximately 2.0 mm in length. Pellets were annealed prior being injection molded, as follows: 2 h @ 175° C. followed by 2 h @ 200° C.

TABLE-US-00003 8 9 10 11 12 PEKK 95 90 83 75 60 PEI 5 10 17 25 40 Tg, 2.sup.nd heat (° C.) 168 170 176 175 183 Tc, 1.sup.st cool (° C.) 282 274 258 266 250 Heat fusion, 2.sup.nd 45 42 36 32 25 heat (J/g)

[0193] PEKK alone has a heat of fusion on 2.sup.nd heat of 48 J/g, whereas 25 wt. % Ultem® (Ex 11) is 32 J/g and 40 wt. % Ultem® (Ex 12) is 25 J/g. These crystallinities ≤32 J/g are too low for printing the part material in a chamber heated at a temperature above the Tg of the blend, which is necessary to induce crystallization in the part. In other words, the 3D printed structures printed from formulations 11 and 12 are not self-supporting. Hence these blends with ΔHf of 32 J/g or less can only be printed by setting the chamber temperature at or below the blend Tg. Under these conditions, the printed part will be essentially amorphous.