Method for manufacturing a three-dimensional object

Abstract

A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising a step consisting in printing layers of the 3D object from the part material comprising a polymeric component comprising, based on the total weight of the polymeric component: from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1):less than 90 mol. % are rigid rod-forming arylene units (R1-a), and at least 10 mol. % are kink-forming arylene units (R1-b), and from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

Claims

1. A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising a step consisting in printing layers of the 3D object from a part material comprising a polymeric component comprising, based on the total weight of the polymeric component: from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1): less than 90 mol. % are arylene units (R1-a), at least 10 mol. % are arylene units (R1-b), wherein (R1-a) is 1,4-phenylene and (R1-b) is 1,3-phenylene; and wherein (R1-a) and (R1-b) are substituted or unsubstituted, and from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

2. The method of claim 1, wherein the polymeric component of the part material comprises: from 5 to 50 wt. % of at least polymer (P1), and from 50 to 95 wt. % of at least polymer (P2).

3. The method of claim 1, wherein the part material also comprises up to 60 wt. %, based on the total weight of the part material, of at least one additive selected from the group consisting of fillers, colorants, lubricants, plasticizers, flame retardants, nucleating agents, flow enhancers and stabilizers.

4. The method of claim 1, wherein P2 is selected from the group consisting of poly(aryl ether sulfone) (PAES) and poly(ether imide) (PEI).

5. The method of claim 1, wherein P2 is a poly(biphenyl ether sulfone) (co)polymer (PPSU).

6. The method of claim 1, wherein P2 is a poly(biphenyl ether sulfone) (co)polymer (PPSU) of Mw ranging from 30,000 to 80,000 g/mol.

7. The method of claim 1, wherein the part material is in the form of a filament or pellets.

8. The method of claim 1, wherein the step of printing layers comprises extruding the part material.

9. The method of claim 1, wherein P2 is a poly(biphenyl ether sulfone) (co)polymer (PPSU) comprising at least 50 mol. % of recurring units (R.sub.PPSU) of formula (K), the mol. % being based on the total number of moles in the polymer: ##STR00056## where R, at each location, is independently selected from a halogen, 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 h, for each R, is independently zero or an integer ranging from 1 to 4.

10. A part material for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising a polymeric component comprising, based on the total weight of the polymeric component: from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1): less than 90 mol. % are arylene units (R1-a), at least 10 mol. % are arylene units (R1-b), wherein (R1-a) is 1,4-phenylene and (R1-b) is 1,3-phenylene; and wherein (R1-a) and (R1-b) are substituted or unsubstituted; and from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

11. The part material of claim 10, wherein P2 is selected from the group consisting of poly(aryl ether sulfone) (PAES) and poly(ether imide) (PEI).

12. A process for manufacturing three-dimensional objects, comprising using a part material comprising a polymeric component comprising, based on the total weight of the polymeric component: from 5 to 95 wt. % of at least one polymer (P1) comprising at least 50 mol. % of recurring units (R1) consisting of an arylene group comprising at least one benzene ring, each recurring unit (R1) being bound to each other through C—C bonds, wherein the recurring units (R1) are such that, based on the total number of moles of recurring units (R1): less than 90 mol. % are arylene units (R1-a), and at least 10 mol. % are arylene units (R1-b), wherein (R1-a) is 1,4-phenylene and (R1-b) is 1,3-phenylene; and wherein (R1-a) and (R1-b) are substituted or unsubstituted, and from 5 to 95 wt. % of at least one polymer (P2), having a glass transition temperature (Tg) between 140° C. and 265° C., and no melting peak, as measured by differential scanning calorimetry (DSC) according to ASTM D3418.

13. The process of claim 12, wherein the part material is in the form of a filament or pellets.

14. The method of claim 1, wherein P1 comprises at least 90 mol % of R1.

15. The method of claim 1, wherein P1 comprises at least 95 mol % of R1.

16. The method of claim 1, wherein P1 comprises at least 99 mol % of R1.

17. The method of claim 1, wherein P1 is a homopolymer consisting of 100 mol % of R1.

18. The method of claim 1, wherein the arylene group is substituted by a monovalent substituting group.

19. The method of claim 18, wherein the monovalent substituting group is selected from the group consisting of: hydrocarbylketones [—C(═O)—R, where R is a hydrocarbyl group], and hydrocarbyloxyhydrocarbylketones [—C(═O)—R.sub.1—O—R.sub.2 where R.sub.1 is a divalent hydrocarbon group and R.sub.2 is a hydrocarbon group].

20. The method of claim 1, wherein P2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 50 mol % of recurring units (R.sub.PPSU) of formula (L″): ##STR00057##

21. The method of claim 1, wherein P2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 95 mol % of recurring units (R.sub.PPSU) of formula (L″): ##STR00058##

22. The method of claim 1, wherein P2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 99 mol % of recurring units (R.sub.PPSU) of formula (L″): ##STR00059##

23. The part material of claim 10, wherein P1 comprises at least 90 mol % of R1.

24. The part material of claim 10, wherein P1 comprises at least 95 mol % of R1.

25. The part material of claim 10, wherein P1 comprises at least 99 mol % of R1.

26. The part material of claim 10, wherein P1 is a homopolymer consisting of 100 mol % of R1.

27. The part material of claim 10, wherein the arylene group is substituted by a monovalent substituting group.

28. The part material of claim 27, wherein the monovalent substituting group is selected from the group consisting of: hydrocarbylketones [—C(═O)—R, where R is a hydrocarbyl group], and hydrocarbyloxyhydrocarbylketones [—C(═O)—R.sub.1—O—R.sub.2 where R.sub.1 is a divalent hydrocarbon group and R.sub.2 is a hydrocarbon group.

29. The part material of claim 10, wherein P2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 95 mol % of recurring units (R.sub.PPSU) of formula (L″): ##STR00060##

30. The part material of claim 10, wherein P2 is a poly(biphenyl ether sulfone) (PPSU) comprising at least 99 mol % of recurring units (R.sub.PPSU) of formula (L″): ##STR00061##

Description

EXAMPLES

(1) The invention 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 invention.

(2) Starting Materials

(3) The following polymers were used to prepare filaments:

(4) Polymer P1: Primospire® PR-250 polyphenylene polymer from Solvay Specialty Polymers

(5) PH: Ultem® 1010, available from Sabic

(6) PPSU #1: a poly(biphenyl ether sulfone) (PPSU) with a Mw of 50,500 g/mol, prepared according to the following process: The synthesis of the PPSU was achieved by the reaction in a 1 L flask of 83.8 g of 4,4′-biphenol (0.450 mol), 131.17 g of 4,4′-dichlorodiphenyl sulfone (0.457 mol) dissolved in a mixture of 400 g of sulfolane with the addition of 66.5 g (0.481 mol) of dry K.sub.2CO.sub.3.

(7) The reaction mixture was heated up to 210° C. and maintained at this temperature until the polymer had the expected Mw. An excess of methyl chloride was then added to the reaction.

(8) The reaction mixture was diluted with 600 g of MCB. The poly(biphenyl ether sulfone) was recovered by filtration of the salts, coagulation, washing and drying. The GPC analysis showed a number average molecular weight (Mw) of 50,500 g/mol, an average molecular weight (Mn) of 21,500 g/mol and PDI index is 2.35.

(9) PPSU #2: a poly(biphenyl ether sulfone) (PPSU) with a Mw of 55,000 g/mol, a Mn of 22,000 g/mol and PDI index is 2.5, prepared according to the same process than PPSU #1, except that the reaction was stopped later.

(10) Irganox® 1010 hindered phenol, product of Clariant.

(11) AMERILUBES XL-165K lubricant, product of Amerilubes.

(12) Blend Compounding

(13) 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:

(14) Barrels 2-6: 190 to 300° C.

(15) Barrels 7-12: 300 to 320° C.

(16) Die: 330° C.

(17) In each case, the resin blends were fed at barrel section 1 using a gravimetric feeder at throughput rates in the range 30-35 lb/hr. The extruder was operated at screw speeds of around 165 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 strand approximately 2.6 to 2.7 mm in diameter and the polymer strand exiting the die was cooled in water and fed to the pelletizer to generate pellets approximately 2.7 mm in length. Pellets were dried at 140° C. for 16 h under vacuum prior to filament processing (FFF, according to the invention) or injection molding (IM, comparative examples).

(18) Filament Preparation

(19) Filaments of diameter of 1.75 mm were prepared for each neat polymer and each blend (see Table 1) using a Brabender® Intelli-Torque Plasti-Corde® Torque Rheometer extruder equipped with a 0.75″ 32 L/D general purpose single screw, a filament head adapter, a 2.5-mm nozzle and ESI-Extrusion Services downstream equipment comprising a cooling tank, a belt puller, and a Dual Station Coiler. A Beta LaserMike® DataPro 1000 was used to monitor filament dimensions. The melt strands were cooled with air. The Brabender® zone set point temperatures were as follows: zone 1, 350° C.; zone 2, 340° C.; zones 3 and 4, 330° C. The Brabender® speed ranged from 30 to 50 rpm and the puller speed from 23 to 37 fpm.

(20) Fused Filament Fabrication Bars (FFF Bars)

(21) Test bars (i.e. ASTM D638Type V bars) were printed from the above filaments of 1.75 mm in diameter on a Hyrel 3D Hydra 430 printer equipped with a 0.6 mm diameter nozzle. Bars were oriented in the XY direction on the build platform during printing. Test bars were printed with a 10 mm-wide brim and three perimeters. The tool path was a cross-hatch pattern with a 45° angle with respect to the long axis of the part. The build plate temperature for all bars was 180° C. The nozzle and extruder temperature was varied from 350° C. to 385° C. The speed of the nozzle was maintained at 40 mm/s except for the first layer which was printed at 20 mm/s. The first layer height in each case was 0.3 mm, with subsequent layers deposited at 0.1 mm height and 100% fill density. The observation of poor printing was made when printing gave bars with obvious gaps and macroscopic voids in material in the majority of layers. Mechanical properties of bars printed poorly were not measured.

(22) Test Methods

(23) Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of the PPSU Polymers

(24) The molecular weight was measured by gel permeation chromatography (GPC), using methylene chloride as a mobile phase. Two 5 μL mixed D columns with guard column from Agilent Technologies were used for separation. An ultraviolet detector of 254 nm was used to obtain the chromatogram. A flow rate of 1.5 ml/min and injection volume of 20 μL of a 0.2 w/v % solution in mobile phase was selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (Peak molecular weight range: 371,000 to 580 g/mol). The weight average molecular weight (Mw) and number average molecular weight (Mn) was reported.

(25) Printing Quality and Impact Strength

(26) Notched impact strength was determined according to the ASTM D256 method using a 2-ftlb hammer.

(27) Tensile Strength

(28) Tensile strength and modulus were determined according to the ASTM D638 method with Type V bars.

(29) The test bars (according to the present invention or comparative) and their mechanical properties are reported in Table 1 below (5 test bars/mean value).

(30) TABLE-US-00003 TABLE 1 1 2 3 4 C : comparative C C I I I : according to the invention Polymer (P1) 100 10 25 PEI PPSU #1 100 90 75 PPSU #2 Irganox ® 1010 0.5 0.3 0.3 0.3 Amerilube 0.5 Process FFF FFF FFF FFF Printing quality − + + + Modulus of Elasticity (GPa) NR 1.76 2.14 2.48 Tensile Strength at Yield (MPa) NR 62 69 75 Nominal Tensile Strain at NR 21 16 17 Break (%) Testing Speed (in/min) 0.05 0.05 0.05 0.05

(31) TABLE-US-00004 TABLE 2 5 6 7 C : comparative I I I I : according to the invention Polymer (P1) 25 50 75 PEI 75 25 PPSU #1 PPSU #2 50 Irganox ® 1010 0.3 0.3 0.3 Process FFF FFF FFF Printing quality + + + Modulus of Elasticity (GPa) 3.12 3.34 4.0 Tensile Strength at Yield (MPa) 103 98 120 Nominal Tensile Strain at 9 16 12 Break (%) Testing Speed (in/min) 0.05 0.05 0.05

(32) NR: not measured as being non relevant

(33) The weight percentages of polymer (P1), PEI and PPSU are based on the total weight of the polymeric component. The weight percentages of the antioxidant and lubricant are based on the total weight of the composition.

(34) According to the literature (e.g. Stratasys TDS), the mechanical properties of PEI printed bars is low compared to all the inventive composition of the invention, more precisely: Modulus of Elasticity (GPa): 2.77 Tensile Strength at Yield (MPa): 64 Nominal Tensile Strain at Break (%): 3.3%

(35) The printing quality is assessed according to two criteria, the appearance of macroscopic voids during printing and the appearance of the fracture surface produced in the Notched Impact test:

(36) (−) means that the test bar could not be printed without the occurrence of macroscopic voids utilizing multiple tool path speeds and extrusion temperatures or that the sample fracture surface presents inter-layer delamination;

(37) (+) means that the sample breaks according to a pattern similar to injection molded parts.

(38) As shown in Table 1, it was not possible to print test bars of reasonable quality by FFF using filaments of polymer (P1). Filaments of PPSU #1 yielded good quality bars, but the bars exhibited low elastic modulus and strength, limiting the usefulness of the material in applications where these properties are important (the same holds true with filaments of polymer PPSU #2, results not shown in Table 1).

(39) The test bars of example 3 and 4 (obtained by FFF with a filament of polymer (P1)/PPSU) yielded good quality bars, exhibit a good modulus of elasticity and a tensile strength that are higher than the test bars of example 2 (obtained by FFF with a filament of neat PPSU).

(40) The test bars of examples 5 and 7 (obtained by FFF with a filament of polymer (P1)/PEI) yielded good quality bars, exhibit a good modulus of elasticity and a tensile strength that are higher than the test bars of example 2 (obtained by FFF with a filament of neat PPSU).

(41) The test bars of example 6, obtained by FFF with a filament of 50 wt. % of polymer (P1) and 50 wt. % of PPSU, yielded good quality bars, exhibit a good modulus of elasticity and a tensile strength that are higher than the test bars of example 2 (obtained by FFF with a filament of neat PPSU).

(42) The present examples demonstrate that the combination of polymer (P1) with PPSU polymer (two different Mw) or the combination of polymer (P1) with PEI is therefore well-suited to the requirements of Fused Filament Fabrication according to the present invention.