NEW POLYAMIDE-CONTAINING POWDERS FOR POWDER BED FUSION PRINTING PROCESS AND PRINTED ARTICLES THEREOF

Abstract

The invention relates to a 3D printable powder composition comprising a polyamide and less than 5 wt % by weight of at least one filler. The invention also relates to the process for preparing the 3D printable powder, and its use for the preparation of a 3D printed article.

Claims

1.-18. (canceled)

19. A 3D printable powder comprising: a polyamide (PA) of the following formula: ##STR00010## wherein: -E- and -J- are identical or different and represent independently from one another a linear or branched, cyclic or acyclic alkylene, or an aromatic bivalent moiety, -G- represents a linear or branched, cyclic or acyclic alkylene, -L- represents —(CH.sub.2).sub.s with s being an integer ranging from 0 to 6, or ##STR00011## -A- represents —(CH.sub.2).sub.r— with r being an integer ranging from 1 to 6, a cyclohexylene group, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, —O—, —O—(CH.sub.2).sub.z—O— with z being an integer ranging from 2 to 12, —O—(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—O—(CH.sub.2).sub.2—O—, —O-Ph-O—, —S—, —S—S—, —S—(CH.sub.2).sub.3—S—, —CO— or —SO.sub.2—, —R1, —R2, —R3, —R4, —R5, —R6, —R7 and —R8 are identical or different and represent independently from one another —H, a (C1-C6) alkyl group, —Cl, —Br, or —I, x is an integer ranging from 0 to 6, y is an integer ranging from 2 to 11, n+p+q=1, provided that p≠0 and q=0, or p=0 and q≠0, or p≠0 and q≠0, and n≥0.1, and less than 5 wt % of at least one filler relative to the weight of the 3D printable powder.

20. The 3D printable powder according to claim 19 wherein the polyamide (PA) is prepared from the following comonomers: a diamine of formula (I): ##STR00012## a diacid of formula (II):
HOOC—(CH.sub.2).sub.y—COOH  (II) and at least one additional comonomer (III) chosen from linear or branched, cyclic or acyclic aliphatic, or aromatic diacids or diamines, or aliphatic aminoacids.

21. The 3D printable powder according to claim 20 wherein the diamine (I) is selected from the group consisting of m-phenylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4, 4′-diaminodiphenyl sulfone, 3,3′-diaminophenyl sulfone, 4,4′-diaminodiphenyl sulphide, 4-aminophenyldisulfide, 4,4′-diaminobenzophenone, 4,4′(ethane-1,2-diylbis(oxy))dianiline, 4,4′(trimethylenedioxy)dianilin, 4,4′-(tetramethylenedioxy)dianiline, 4,4′-(pentamethylenedioxy)dianiline, 4,4′-(hexamethylenedioxy)dianiline, 4,4′-dodecanediyldioxy-di-aniline, 2,2′-[1,2-ethanediylbis(oxy-2,1-ethanediyloxy)]dianiline, 3,3′-[1,4-phenylenebis(oxy)]dianiline, 2,2′-(1,3-propanediyldisulfanediyl)dianiline, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-(propane-2,2,diyl)dianiline, 4,4′-cyclohexylidene dianiline, and 4,4′-(hexafluoroisopropylidene)dianiline.

22. The 3D printable powder according to claim 20 wherein the diacid (II) is selected from the group consisting of sebacic acid, adipic acid and dodecandioic acid.

23. The 3D printable powder according to claim 20 wherein the polyamide (PA) is prepared from diamine (I), diacid (II) and from 1 to 90 mol % of at least one additional comonomer (III).

24. The 3D printable powder according to claim 23 wherein the at least one additional comonomer (III) is selected from the group consisting of a diamine, a diacid, and an aminoacid.

25. The 3D printable powder according to claim 19 wherein the polyamide (PA) has an average molecular weight by number Mn of at least 10 000 g.Math.mol.sup.−1.

26. The 3D printable powder according to claim 19 comprising less than 2 wt % of filler(s) relative to the weight of the 3D printable powder.

27. The 3D printable powder according to claim 19 futher comprising at least one additive selected from the group consisting of flow aid(s), retarding agent(s), impact modifier(s), antioxidant(s), co-crystallizer(s), plasticizer(s), dye(s), thermal stabilizer(s), antistatic agent(s), waxe(s), anti-nucleating agent(s) and compatibilizer(s).

28. A process for the preparation of the 3D printable powder according to claim 19 comprising preparing the polyamide (PA) by polycondensation and a step of mixing with the at least one filler if present.

29. The process according to claim 28 wherein the polyamide (PA) is prepared according to the following steps that are carried out in a reactor: i) formation of a salt (A) from diamine (I), diacid (II) and additional comonomer(s) (III), ii) heating of the salt (A) under pressure, iii) removing the water.

30. The process according to claim 28 wherein the polyamide (PA) is prepared according to the following steps: a) introduction of diamine (I), diacid (II) and additional comonomer(s) (III) into an extruder including at least two conveying screws rotating co-rotatively, b) mixing the comonomers, c) polycondensing the comonomers by successively carrying out shearing and depressurization operations on the material conveyed by the conveying screws, d) forming a plug of material continuously renewed by conveyance of the material on the conveying screws, between the mixing and polycondensation steps; said material plug consisting of the advancing material filling the whole space available for the passage of the material and forming an area which is hermetic to vapors, and notably to monomer vapors which may be generated.

31. The process according to claim 28 wherein the polyamide (PA) is prepared according to the following steps: a′) introduction of a polymer (P) into an extruder including at least two conveying screws rotating co-rotatively, said polymer (P) being a homopolymer or copolymer of diamine (I) and/or diacid (II) and/or additional comonomer(s) (III), b′) introduction of at least one comonomer selected from diamine (I), diacid (II) and additional comonomer(s) (III) into said extruder, c′) mixing the polymer (P) and the at least one conomoner, d′) polycondensing the polymer (P) and the comonomer(s) by successively carrying out shearing and depressurization operations on the material conveyed by the conveying screws, e′) forming a plug of material continuously renewed by conveyance of the material on the conveying screws, between the mixing and polycondensation steps; said material plug consisting of the advancing material filling the whole space available for the passage of the material and forming an area which is hermetic to vapors, and notably to monomer vapors which may be generated.

32. A three-dimensional printed article made from the 3D printable powder according to claim 19.

33. The three-dimensional printed article according to claim 32 having a Young modulus of at least 2000 MPa measured according to NF EN ISO 527-2 and ASTM D638-08 standards.

34. The three-dimensional printed article according to claim 32 having a strength at break of at least 45 MPa measured according to NF EN ISO 527-2 and ASTM D638-08 standards.

35. A method for preparing a three-dimensional printed article according to claim 32 using a powder bed fusion process.

36. A method comprising manufacturing a three dimensional printed article comprising 3D printing with the printable powder according to claim 19.

37. The 3D printable powder according to claim 23 wherein the at least one additional comonomer (III) is selected from the group consisting of hexamethylene diamine, trimethylhexamethylene diamine, 4,4′-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,2-diaminocyclohexane, isophorone diamine, decane diamine, hexanoic diacid, nonanoic diacid, decanoic diacid, dodecanoic diacid, aminohexanoic acid, 11-aminoundecanoic acid and 13-aminotridecanoic acid.

Description

EXAMPLES

[0210] In the following examples: [0211] the melt viscosity rates (MVR) are measured with a melt flow indexer at 240° C. under 2.14 kg according to ISO 1133:2011 standard; [0212] the granulometries of the 3D printable powders are measured with a granulometer Mastersizer 3000 from Malvern; [0213] the Hausner ratio and the initial bulk density of the 3D printable powders are determined with a granular material density analyzer (GranuPack from GranuTools™) using a tapped density measurement test; [0214] Young modulus, stress at break, stress at yield, strain at yield and strain at break are measured according to NF EN ISO 527-2 and ASTM D638-08 standards.

Example 1

[0215] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol.sup.−1) and sebacic acid (202.25 g.Math.mol.sup.−1) were polymerized using process described in patent application WO 2014/016521 to produce a polyamide PA1 with a MVR of 33 cm.sup.3/10 min.

[0216] Polyamide PA1 was produced from 22070 g of m-xylylenediamine, 31800 g of sebacic acid and 50.88 g of phosphoric acid (H.sub.3PO.sub.4). No filler or other additive was added to polyamide PA1.

[0217] A twenty kilograms sample was grinded using a cryo-milling equipment (Godding and Dressler), mixed with 0.25% Cabosil M5 and sieved (90 μm) to afford a 3D printable powder PP1 according to the invention.

[0218] The Hausner ratio of 3D printable powder PP1 is of 1.175 [Ø] with an initial bulk density of 0.462 g.Math.cm.sup.3.

[0219] Four kg of 3D printable powder PP1 were used to prepare a 3D printed article by laser sintering printing using a Formiga P110 sold by EOS. The laser parameters used were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: the chamber temperature was 177° C. and the tank temperature was 150° C.

[0220] H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with a good dimensional stability (no bending) after the end of printing.

Example 2

[0221] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol.sup.−1) and sebacic acid (202.25 g.Math.mol.sup.−1) were polymerized using the process described in patent application WO 2014016521 to produce a polyamide PA2 with a MVR of 25 cm.sup.3/10 min.

[0222] Polyamide PA2 was produced from 22070 g of m-xylylenediamine, 31800 g of sebacic acid, and 50.88 g of phosphoric acid (H.sub.3PO.sub.4). No filler or other additive was added to polyamide PA2.

[0223] A twenty kilograms sample was grinded using a continuous cryo-miller (GSM 250 from Gotic) equipped with a 90 μm sieve. Powdered polyamide PA2 was then mixed with 0.25 wt % of fumed silica (AEROSIL® R812 sold by EVONIK) to afford 3D printable powder PP2.1.

[0224] The Hausner ratio of 3D printable powder PP2.1 is of 1.216 [Ø] with an initial bulk density of 0.463 g.Math.cm.sup.3.

[0225] Four kg of 3D printable powder PP2.1 were used to prepare a 3D printed article by laser sintering printing using a Formiga P110 from EOS. The laser parameters were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: chamber temperature at 175° C. and tank temperature at 130° C.

[0226] H1 tensile specimen (ISO 527) were printed and unpacked from the building “cake” with a good dimensional stability (no bending) after the end of printing.

[0227] Powdered polyamide PA2 was also mixed with 0.5 wt % of another fumed silica (CABOSIL® M5 from Cabot Corporation) to afford 3D printable powder PP2.2.

[0228] The Hausner ratio of 3D printable powder PP2.2 is of 1,192 [Ø] and the initial bulk density is of 0.529 g.Math.cm.sup.3.

[0229] Ten kg of 3D printable powder PP2.2 were used to prepare a 3D printed article by laser sintering using a Prodways Promaker P1000 sold by EOS. The used laser parameters were as follows: power at 14.7 W/12 W, hatching distance at 0.15 mm/0.15 mm, speed at 3500 mm.Math.second. The used printer parameters were as follows: the chamber temperature was 175.5° C. (front) and 177.5° C. (back), the piston temperature was of 150° C., the three heating belts of the chamber were at 140° C. and the feeder temperature was of 80° C.

[0230] H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with a good dimensional stability (no bending) after the end of printing.

Example 3

[0231] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol.sup.−1) and sebacic acid (202.25 g.Math.mol.sup.−1) were polymerized using process described in patent application WO 2014/016521 to produce a polyamide PA3 with a MVR of 25 cm.sup.3/10 min.

[0232] The polyamide was produced from 22070 g of m-xylylenediamine, 31800 g of sebacic acid and 50.88 g of phospohoric acid (H.sub.3PO.sub.4). No filler or other additive was added to polyamide PA3.

[0233] A twenty kilograms sample was grinded using a continuous cryo-miller (GSM 250 from Gotic) equipped with a 90 μm sieve. Powdered polyamide PA3 was mixed with 0.25 wt % of fumed silica (AEROSIL® R812 from EVONIK) and dried at 110° C. under vacuum during 2 hours (final moisture 0.4%) to afford 3D printable powder PP3.

[0234] The Hausner ratio of 3D printable powder PP3 is of 1.23 [Ø] with an initial bulk density of 0.44 g.Math.cm.sup.3.

[0235] Five kg of 3D printable powder PP3 were used to prepare a 3Dprinted article by laser sintering printing using a Formiga P110 from EOS. The laser parameters were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: chamber temperature at 175° C. and tank temperature at 130° C.

[0236] H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with a good dimensional stability (no bending) after the end of printing.

Example 4

[0237] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol-1), hexamethylene diamine (116.21 g.Math.mol-1) and sebacic acid (202.25 g.Math.mol.sup.−1) were polymerized using the process described in patent application WO 2014/016521 to produce a polyamide PA4 with a MVR of 37 cm.sup.3/10 min.

[0238] Polyamide PA4 was produced from 13555 g of m-xylylenediamine, 1285 g of hexamethylene diamine, 20450 g of sebacic acid and 32.72 g of phosphoric acid. Hexamethylene diamine represents 10% (mol/mol) of diamine content. No filler or other additive was added to polyamide PA4.

[0239] A twenty kilograms sample is grinded a continuous cryo-miller (GSM 250 from Gotic) equipped with a 90 μm sieve. Powdered polyamide PA4 was then mixed with 0.25 wt % of fumed silica (AEROSIL® R812 sold by EVONIK) to afford 3D printable powder PP4.

[0240] The Hausner ratio of 3D printable powder PP4 is of 1.299 [Ø] with an initial bulk density of 0.488 g.Math.cm.sup.3.

[0241] Four kg of 3D printable powder PP4 were used to prepare a 3D printed article by laser sintering printing using a Formiga P110 from EOS. The laser parameters were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: chamber temperature at 173° C. and tank temperature at 130° C.

[0242] H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with a good dimensional stability (no bending) after the end of printing.

Example 5

[0243] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol.sup.−1), trimethylhexamethylene diamine (158.28 g.Math.mol.sup.−1) and sebacic acid (202.25 g.Math.mol.sup.−1) were polymerized using process described in patent application WO 2014/016521 to produce a polyamide PA5 with a MVR of 15 cm.sup.3/10 minutes.

[0244] Polyamide PA5 was produced from 14394 g of m-xylylenediamine, 880 g of trimethylhexamethylene diamine, 20450 g of sebacic acid and 32.72 g of phosphoric acid (H.sub.3PO.sub.4). Trimethylhexamethylene diamine represents 5% (mol/mol) of the diamine content. No filler or other additive was added to polyamide PA5.

[0245] A twenty kilograms sample was grinded using a continuous cryo-miller (GSM 250 from Gotic) equipped with a 100×300 μm sieve. Powdered polyamide PA5 was then mixed with fumed silica (0.2 wt % of Cabosil® M5 from Cabot Corporation U.S.A. and 0.2 wt % Aerosil R812 from Evonik) to afford 3D printable powder PP5.

[0246] The Hausner ratio of 3D printable powder PP5 is of 1.233 [Ø] with an initial bulk density of 0.471 g.Math.cm.sup.3.

[0247] Four kg of 3D printable powder PP5 were used to prepare a 3D printed article by laser sintering printing using a Formiga P110 from EOS. The laser parameters were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: chamber temperature at 171° C. and tank temperature at 135° C.

[0248] H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with an excellent dimensional stability (no bending) after the end of printing.

Example 6

[0249] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol.sup.−1), trimethylhexamethylene diamine (158.28 g.Math.mol.sup.−1) and sebacic acid (202.25 g.Math.mol.sup.−1) were polymerized using process described in patent application WO 2014/016521 to produce a polyamide PA6 with a MVR of 45 cm.sup.3/10 min.

[0250] Polyamide PA6 was produced from 11974 g of m-xylylenediamine, 3479 g of trimethylhexamethylene diamine, 206900 g of sebacic acid, and 33.1 g of phosphoric acid (H.sub.3PO.sub.4). Trimethylhexamethylene diamine represents 20% (mol/mol) of the diamine content. No filler or other additive was added to polyamide PA6.

[0251] A twenty-five kilograms sample was grinded using a continuous cryo-miller (GSM 250 from Gotic) equipped with a 100×300 μm sieve. Powdered polyamide PA6 was then mixed with fumed silica (0.2 wt % of Cabosil® M5 from Cabot Corporation U.S.A. and 0.2 wt % Aerosil R812 from Evonik) to afford 3D printable powder PP6.

[0252] The Hausner ratio of 3D printable powder PP6 is of 1.202 [Ø] with a bulk density of 0.427 g.Math.cm.sup.3.

[0253] Four kg of this 3D printable powder PP6 were used to prepare a 3D article by laser sintering printing using a Formiga P110 from EOS. The laser parameters were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: chamber temperature at 154° C. and tank temperature at 130° C.

[0254] Seven H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with an excellent dimensional stability (no bending) after the end of printing.

Example 7

[0255] Using a 110 L/D (diameter: 32 mm) twin-screw extruder as continuous reactor, m-xylylenediamine (136.19 g.Math.mol.sup.−1), sebacic acid (202.25 g.Math.mol.sup.−1) and polyamide 10,10 (MVR of 18 cm.sup.3/10 min at 240° C.) were introduced and polycondensed using process described in patent application WO 2014/016521. A polyamide PA7 with a MVR of 18 cm.sup.3/10 min is obtained. The polyamide 10,10 was previously prepared from sebacic acid (202.25 g.Math.mol.sup.−1 and 1-10 decanediamine (172.31 g.Math.mol.sup.−1) using process described in patent application WO 2014/016521.

[0256] Polyamide PA7 was produced from 4451 g of m-xylylenediamine, 6368 g of sebacic acid, 25300 g of polyamide 10,10 and 33.1 g of phosphoric acid (H.sub.3PO.sub.4). Polyamide 10,10 represents 70% (g/g) of the reaction media content. No filler or other additive was added to polyamide PA7.

[0257] A twenty-five kilograms sample was grinded using a continuous cryo-miller (GSM 250 from Gotic) equipped with a 125×125 μm sieve. Powdered polyamide PA7 was then mixed with fumed silica (0.2 wt % of Cabosil® M5 from Cabot Corporation and 0.2 wt % Aerosil R812 from Evonik to afford 3D printable powder PP7.

[0258] The Hausner ratio of 3D printable powder PP7 is of 1.23 [Ø] with an initial density of 0.52 g.Math.cm.sup.3.

[0259] Four kg of this 3D printable powder PP7 were used to prepare a 3D article by laser sintering printing using a Formiga P110 from EOS. The laser parameters were as follows: power at 12 W/14 W, hatching distance at 0.15 mm, speed at 3500 mm.Math.second. The printer parameters were as follows: chamber temperature at 177° C. and tank temperature at 150° C.

[0260] Seven H1 tensile specimens (ISO 527) were printed and unpacked from the building “cake” with an excellent dimensional stability (no bending) after the end of printing.

Example 8

[0261] The properties of the 3D printable powders of the invention and the printed part thereof are illustrated in tables 1 to 4 below.

[0262] The granulometry of 3D printable powders PP1, PP2.1, PP2.2, PP3, PP4, PP5, PP6 and PP7 is reported in table 1 below.

TABLE-US-00001 TABLE 1 D10 D50 D90 D99 PA1 22.9 μm 52.1 μm 93.5 μm 130 μm PP2.1 13.8 μm 35.5 μm 66.2 μm 94 μm PP2.2 13.8 μm 35.5 μm 66.2 μm 94 μm PP3 14.8 μm 34.5 μm 61.6 μm 85.3 μm PP4 12.5 μm 33.7 μm 63.9 μm 91.2 μm PP5 17.9 μm 52.4 μm 105 μm 154 μm PA6 26.9 μm 65 μm 124 μm 179 μm PA7 16.6 μm 44.6 μm 83.7 μm 119 μm

[0263] All 3D printable powders have satisfactory granulometry.

[0264] The mechanical properties of 3D printed parts obtained from the exemplified 3D printable powders are reported in table 2. The results were obtained after a 48 h conditioning at 23° C. and 50% relative humidity for 3D printable powders PP1, PP2.1, PP2.2, PP4, PP5, PP6 and PP7, and after (A) 336 h at 80° C. under vacuum and (B) 336 h at 70° C. at 62% humidity for PP3.

TABLE-US-00002 TABLE 2 Young modulus Stress at Strain at Stress at Strain at (MPa) yield (MPa) yield (%) break (MPa) break (%) PP1 3900 +/− 71 +/− 2.8 +/− 8 2 0.12 PP2.1 3740 +/− — — 70 +/− 3 +/− 22 2 0.09 PP2.2 3870 +/− — — 73.5 +/− 3.2 +/− 31 10 0.6 PP3 3816 +/− — — 75 +/− 2.6 +/− (A) 101 4 0.3 PP3 3663 +/− — — 61 +/− 2.3 +/− (B) 87 6 0.5 PP4 3780 +/− — — 80 +/− 3.7 +/− 29 1 0.15 PP5 3790 +/− — — 70 +/− 3.0 +/− 22 3 0.16 PP6 3320 +/− — — 53 +/− 2.4 +/− 40 2 0.22 PP7 2010 ± 59.8 ± 4.0 ± 46.1 ± 10 ± 15 0.7 0.03 1 0.73

[0265] All 3D printed articles obtained from the exemplified 3D printable powders have Young modulus of at least 2 GPa. Compared to 3D printable powders from examples 1 to 6, 3D printable powder PP7 allows an improved elongation at break of 10% while having a modulus of 2000 MPa.

[0266] Recycling of PP1 has also been studied (by using 100% of recycled powder for the printing) and the mechanical properties after each cycle have been evaluated. Results are reported with the melt viscosity in table 3 below.

TABLE-US-00003 TABLE 3 Young Stress at break Strain at break Melt viscosity Cycle modulus (MPa) (MPa) (%) (cm.sup.3/10 min) 1 3900 ± 8 71 ± 2 2.8 ± 0.12 21 2 3880 ± 31 69 ± 6 2.5 ± 0.26 30 3 3860 ± 36 68 ± 4 2.7 ± 0.24 26 4 3840 ± 30 71 ± 5 2.9 ± 0.31 21 5 3930 ± 55 77 ± 4 3.1 ± 0.26 15 6 3880 ± 38 72 ± 4 2.9 ± 0.24 26 7 3820 ± 29 69 ± 4 2.8 ± 0.23 19

[0267] As shown in table 3, the mechanical properties are good and conserved after 7 cycles without addition of new powder.

[0268] The thermal behaviour of 3D printable powders PP1, PP2, PP3, PP4, PP5, PP6 and PP7 were determined by DSC scan (10° C./min). Results are reported in table 4 below.

TABLE-US-00004 TABLE 4 Onset Onset Melting crystal- Crystal- En- melting peak lization lization thalpy temper- temper- temper- temper- of ature ature ature ature fusion PP1 181° C. 192° C. 144° C. 129° C. 44 J/g PP2 182° C. 192° C. 147° C. 138° C. 42 J/g PP3 182° C. 192° C. 146° C. 135° C. 42 J/g PP4 176° C. 187° C. 143° C. 133° C. 39 J/g PP5 176° C. 186.5° C. 140.8° C. 122° C. 45 J/g PP6 166.7° C. 176.2° C. — — 20 J/g PP7 176.1° C. 191.3° C. 153.3° C. 144.6° C.   54 J/g

[0269] Compared to 3D printable powders from examples 1 to 5, 3D printable powder PP6 containing 20% of amine comonomer III has a reduced crystallization rate and the onset crystallization temperature and the peak could not be measured.