POWDERED MATERIAL (P) CONTAINING POLY(ARYLENE SULFIDE) (PAS) POLYMER AND ITS USE FOR ADDITIVE MANUFACTURING

Abstract

The present invention relates to a powdered material (M) containing at least one poly(arylene sulfide) (PAS) polymer, comprising recurring units p, q and r according of formula (I) wherein n.sub.p, n.sub.q and n.sub.r are respectively the mole % of each recurring units p, q and r; recurring units p, q and r are arranged in blocks, in alternation or randomly; 2≤(n.sub.q+n.sub.r)/(n.sub.p+n.sub.q+n.sub.r)≤9; nq is ≥0% and nr is ≥0%; j is zero or an integer varying between 1 and 4; R.sup.1 is selected from the group consisting of halogen atoms, C.sub.1-C.sub.12 alkyl groups, C.sub.7-C.sub.24 alkylaryl groups, C.sub.7-C.sub.24 aralkyl groups, C.sub.6-C.sub.24 arylene groups, C.sub.1-C.sub.12 alkoxy groups, and C.sub.6-C.sub.18 aryloxy groups.

##STR00001##

Claims

1-15. (canceled)

16. A powdered material (M) for additive manufacturing, comprising: one polymeric component (P) comprising at least one poly(arylene sulfide) (PAS) polymer, comprising recurring units p, q and r according of formula (I): ##STR00007## n.sub.p, n.sub.q and n.sub.r are respectively the mole % of each recurring units p, q and r; recurring units p, q and r are arranged in blocks, in alternation or randomly; 2%≤(n.sub.q+n.sub.r)/(n.sub.p+n.sub.q+n.sub.r)≤9%; n.sub.q is ≥0% and n.sub.r is ≥0%; j is zero or an integer varying between 1 and 4; R.sup.1 is selected from the group consisting of halogen atoms, C.sub.1-C.sub.12 alkyl groups, C.sub.7-C.sub.24 alkylaryl groups, C.sub.7-C.sub.24 aralkyl groups, C.sub.6-C.sub.24 arylene groups, C.sub.1-C.sub.12 alkoxy groups, and C.sub.6-C.sub.18 aryloxy groups, optionally one or several flow agent(s) (F), optionally one or several additive(s) (A) selected from the group consisting of lubricants, heat stabilizers, light stabilizers, antioxidants, pigments, processing aids, dyes, fillers, nanofillers or electromagnetic absorbers and flame retardants.

17. The powdered material (M) of claim 16, wherein the PAS is such that n.sub.p+n.sub.q+n.sub.r≥50%.

18. The powdered material (M) of claim 16, wherein the PAS is such that it consists essentially of recurring units p, and recurring units q and/or r.

19. The powdered material (M) of claim 16, wherein the PAS is such that j is zero in formula (I).

20. The powdered material (M) of claim 16, wherein the PAS has a heat of fusion of more than 20 J/g, determined on the 2.sup.nd heat scan in differential scanning calorimeter (DSC) according to ASTM D3418, using heating and cooling rates of 20° C./min.

21. The powdered material (M) of claim 16, wherein the PAS is such that it has a melting point of at most 280° C., and/or of at least 240° C., when determined on the 2.sup.nd heat scan in differential scanning calorimeter (DSC) according to ASTM D3418, using heating and cooling rates of 20° C./min.

22. The powdered material (M) of claim 16, wherein the flow agent (F) is an inorganic pigment selected from the group consisting of silicas, aluminas and titanium oxide.

23. The powdered material (M) of claim 16, wherein the flow agent (F) is fumed silica.

24. The powdered material (M) of claim 16, wherein the material (M) has a d.sub.0.5-value ranging between 15 and 80 μm, as measured by laser scattering in isopropanol.

25. A process for manufacturing a three-dimensional (3D) article, part or composite material, comprising: a) depositing successive layers of a powdered material (M) of claim 16, and b) printing layers prior to deposition of the subsequent layer.

26. The process of claim 25, wherein step b) comprises selective sintering by means of an electromagnetic radiation of the powder.

27. A three-dimensional (3D) article, part or composite material obtained by additive manufacturing from the powdered material (M) of claim 16.

28. A method for manufacturing a three-dimensional (3D) object, the method comprising using the powdered material (M) of claim 16 in an additive manufacturing process to form the three-dimensional (3D) object.

29. A method for manufacturing a powdered material (M), the method comprising using a polymeric component (P) comprising at least one poly(arylene sulfide) (PAS) polymer, comprising recurring units p, q and r according of formula (I): ##STR00008## wherein n.sub.p, n.sub.q and n.sub.r are respectively the mole % of each recurring units p, q and r; recurring units p, q and r are arranged in blocks, in alternation or randomly; 2%≤(n.sub.q+n.sub.r)/(n.sub.p+n.sub.q+n.sub.r)≤9%; n.sub.q is ≥0% and n.sub.r is ≥0%; j is zero or an integer varying between 1 and 4; R.sup.1 is selected from the group consisting of halogen atoms, C.sub.1-C.sub.12 alkyl groups, C.sub.7-C.sub.24 alkylaryl groups, C.sub.7-C.sub.24 aralkyl groups, C.sub.6-C.sub.24 arylene groups, C.sub.1-C.sub.12 alkoxy groups, and C.sub.6-C.sub.18 aryloxy groups, optionally in combination with one or several flow agent(s) (F) and/or one or several additives (A), to manufacture the powdered material (M).

30. A method for using the article, part or composite material of claim 27, the method comprising using the article, part or composite in an oil and gas application, an automotive application, an electric and electronic application, or aerospace and consumer goods application.

Description

EXPERIMENTAL SECTION

[0096] Materials

[0097] Ryton® QA200N is a poly(phenylene sulfide) commercially available from Solvay Specialty Polymers USA.

[0098] Hydrogen peroxide 30% w/w aqueous solution was purchased from Fischer.

[0099] Acetic acid with purity of 99% was purchased from VWR.

Synthesis Example

[0100] PAS Polymer #1 (Inventive)

[0101] Ryton® QA200N (200 g, 1.0 eq) was suspended in acetic acid (400 mL) under a nitrogen atmosphere inside a 1 L reactor equipped with an inclined quadripale type stirrer, a condenser, a double jacket for heating and a syringe pump.

[0102] The resulting suspension was stirred at room temperature and hydrogen peroxide 30% w/w (6.0 g, 0.03 eq) was added via syringe pump over a period of 15 minutes.

[0103] The temperature was raised to 70° C. (double jacket set at 75° C.) and the reaction mixture was stirred for 3 hours at this temperature. The stirring speed was set to 300 rpm. Then, an analysis of the supernatant with Quantofix peroxide test sticks confirmed the absence of peroxide.

[0104] The reaction mixture was then cooled to room temperature and filtered. The recovered solids were washed twice with acetic acid at room temperature (2×100 mL). The solids were then dried in a rotating evaporator under a pressure of 20 mbar and at a temperature of 50° C. for 2 hours. The recovered solids were than dried under vacuum (˜20 mbar) at 120° C. for 7 hours.

[0105] The obtained product is a poly(phenylene sulfide) of formula (I), wherein j=0, n.sub.p=96%, n.sub.q+n.sub.r=4%. Accordingly, under these conditions 4 mol. % of the sulfide moieties of Ryton® QA200N have been oxidized into sulfoxide and sulfone moieties.

[0106] Characterization of the Polymeric Component

[0107] DSC/Heat of Fusion

[0108] DSC analyses were carried out on DSC Q200-5293 TA Instrument according to ASTM D3418 and data was collected through a two heat, one cool method. The protocol used is the following: 1st heat cycle from 30.00° C. to 350.00° C. at 20.00° C./min; isothermal for 5 minutes; 1st cool cycle from 350.00° C. to 30.00° C. at 20.00° C./min; 2.sup.nd heat cycle from 30.00° C. to 350.00° C. at 20.00° C./min. The melting temperature (T.sub.m) is recorded during the 1.sup.st and 2.sup.nd heat cycles, the melt crystallization temperature (T.sub.mc) is recorded during the cool cycle, the glass transition temperature (T.sub.g) is recorded during the 2.sup.nd heat cycle, and the enthalpy of melting (ΔH) is recorded during the 2.sup.nd heat cycle.

[0109] Grinding of the Polymeric Components—Preparation of the Powdered Materials

[0110] Ryton® QA200N (comparative) and PAS polymer #1 (inventive) were turned into powders by milling on a rotor attrition mill (Retsch Rotor Mill SR300) and characterized. Results are presented in Table 1.

[0111] The powders were then blended with 0.3% fumed silica (Cab-O-Sil® M-5 from Cabot Corporation) via drum rolling and sieved through No. 120 mesh tensile bolting cloth (pore size of 147 μm).

[0112] PSD

[0113] Particle size (d.sub.10, d.sub.50 and d.sub.90) was determined on the final powders by an average of 3 runs via a laser scattering technique on a Microtrac S3500 analyzer in wet mode (128 channels, between 0.0215 and 1408 μm). The solvent used was isopropanol with a refractive index of 1.38, with the particles assumed to have a refractive index of 1.59. The ultrasonic mode was enabled (25 W/60 seconds) and the flow was set at 55%. Results are presented in Table 2 below.

[0114] BET Surface Area and Bulk Density

[0115] BET surface area (multi-point) of the final powders was determined on a TriStar II Plus Version 3.01 surface area and pore analyzer via nitrogen (N2) gas adsorption according to ISO 9277. Bulk density of the powders was determined via Method A of ASTM D1895. Results are presented in Table 2 below.

TABLE-US-00001 TABLE 1 Oxidized T.sub.m Tm moieties T.sub.g T.sub.mc 2.sup.nd heat 1.sup.st heat ΔH [mol. %] (° C.) (° C.) (° C.) (° C.) (J .Math. g.sup.−1) Ryton ® 0 94.6 226.9 279.6 289.4 50.9 QA200N PAS 4 100.9 150.1 252.3 285.3 23.1 polymer #1

TABLE-US-00002 TABLE 2 BET Surface Bulk Density PSD Area (m.sup.2/g) (g/cm.sup.3) (microns) Comparative 1.83 0.64 d.sub.10: 33 powder (based on d.sub.50: 50 Ryton ® QA200N) d.sub.90: 79 Inventive powder 3.82 0.67 d.sub.10: 30 (based on PAS d.sub.50: 48 polymer #1) d.sub.90: 78

[0116] Printing

[0117] Printing occurred on an EOSINT® P800 SLS Printer, using the following print settings: hatch laser power of 17 watts, contour laser power of 8.5 watts, laser speed of 2.65 m/s, and cooling rate after print completion of less than 10° C./min.

[0118] The powdered materials were sintered into ASTM Type I tensile bars.

[0119] Characterization of the Printed Bars

[0120] The ASTM Type I tensile bars were tested according to ASTM D638, where the result reported in Table 3 is an average from 5 bars.

[0121] Results

TABLE-US-00003 TABLE 3 Ultimate Tensile Processing Tensile Elongation PSD Temperature Strength at Break Example (microns) (° C.) (MPa) (%) Comparative d.sub.10: 33 275 48 1.4 powder (based on d.sub.50: 50 Ryton ® QA200N) d.sub.90: 79 Inventive powder d.sub.10: 30 263 55 2.4 (based on PAS d.sub.50: 48 polymer #1) d.sub.90: 78

[0122] The powder comprising unmodified PPS Ryton® QA200N (comparative powder) was first printed at a processing temperature of 263° C., but this led to curling. The processing temperature of the comparative powder was thus adjusted to 275° C. to avoid curling. The powder based on the inventive PAS polymer #1 was printed at a processing temperature of 263° C. and no curling occurred.

[0123] The inventive powder demonstrated better printing characteristics and final resulting printed part properties (mechanical and part aesthetics) than the comparative powder. During the print, the inventive powder demonstrated a smooth bed surface during the entire print. This is critical towards obtaining a stable print that will result in a successful print completion and acceptable parts.

[0124] The bars printed from the inventive powder exhibited smooth surfaces.

[0125] The use of the inventive powder resulted in parts with mechanical properties (both ultimate tensile strength and tensile elongation at break) superior to that of the unmodified Ryton® QA200N.