阅读说明：本技术 含有聚(亚芳基硫醚)(pas)聚合物的粉末状材料(p)及其用于增材制造的用途 (Powdered material (P) containing poly (arylene sulfide) (PAS) polymers and use thereof for additive manufacturing ) 是由 C·沃德 S·乔尔 B·吉尔肯森 陈虹 于 2020-04-07 设计创作，主要内容包括：本发明涉及包含至少一种聚(亚芳基硫醚)(PAS)聚合物的粉末材料(M),所述聚合物包含根据式(I)的重复单元p、q和r：其中n-(p)、n-(q)和n-(r)分别为每个重复单元p、q和r的摩尔％；重复单元p、q和r以嵌段方式、以交替方式或无规地排列；2≤(n-(q)+n-(r))/(n-(p)+n-(q)+n-(r))≤9；n-(q)是≥0％并且n-(r)是≥0％；j是零或在1与4之间变化的整数；R～(1)选自由以下组成的组：卤素原子、C-(1)-C-(12)烷基、C-(7)-C-(24)烷基芳基、C-(7)-C-(24)芳烷基、C-(6)-C-(24)亚芳基、C-(1)-C-(12)烷氧基、和C-(6)-C-(18)芳氧基。(The present invention relates to a powdered material (M) comprising at least one poly (arylene sulfide) (PAS) polymer comprising recurring units p, q and r according to formula (I): wherein n is p 、n q And n r Mole% of each repeating unit p, q, and r, respectively; the repeating units p, q and r are arranged in a block manner, in an alternating manner or randomly; 2 is less than or equal to (n) q +n r )/(n p +n q +n r )≤9；n q Is not less than 0% and n r Is more than or equal to 0 percent; j is zero or an integer varying between 1 and 4; r 1 Selected from the group consisting of: halogen atom, C 1 ‑C 12 Alkyl radical, C 7 ‑C 24 Alkylaryl group, C 7 ‑C 24 Aralkyl radical, C 6 ‑C 24 Arylene radical, C 1 ‑C 12 Alkoxy, and C 6 ‑C 18 An aryloxy group.)

1. A powdered material (M) for additive manufacturing, comprising:

-a polymer component (P) comprising at least one poly (arylene sulfide) (PAS) polymer comprising recurring units P, q and r according to formula (I):

wherein

n_p、n_qAnd n_rMole% of each repeating unit p, q, and r, respectively;

the repeating units p, q and r are arranged in a block manner, in an alternating manner or randomly;

2％≤(n_q+n_r)/(n_p+n_q+n_r)≤9％；n_qis not less than 0% and n_rIs more than or equal to 0 percent;

j is zero or an integer varying between 1 and 4;

R¹selected from the group consisting of: halogen atom, C₁-C₁₂Alkyl radical, C₇-C₂₄Alkylaryl group, C₇-C₂₄Aralkyl radical, C₆-C₂₄Arylene radical, C₁-C₁₂Alkoxy, and C₆-C₁₈An aryloxy group which is a group having a lower alkoxy group,

optionally one or several glidants (F),

-optionally, one or several additives (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.

2. The powdery material (M) of claim 1, wherein PAS is such that n_p+n_q+n_r≥50％。

3. The powdery material (M) according to claim 1 or 2, wherein the PAS is such that it consists of, or essentially consists of, repeating units p, and repeating units q and/or r.

4. The powdery material (M) of any of claims 1 to 3, wherein the PAS is such that j in formula (I) is zero.

5. The powdery material (M) of any of claims 1 to 4, wherein the PAS has a heat of fusion of more than 20J/g, as determined according to ASTM D3418 using a heating and cooling rate of 20 ℃/min on the 2 nd thermal scan in a Differential Scanning Calorimeter (DSC).

6. The powdery material (M) of any of claims 1 to 5, wherein the PAS is such that it has a melting point of at most 280 ℃, preferably at most 278 ℃, more preferably at most 275 ℃, and/or at least 240 ℃, preferably at least 248 ℃, more preferably at least 250 ℃, when determined according to ASTM D3418 using a heating and cooling rate of 20 ℃/min in the 2 nd thermal scan in a Differential Scanning Calorimeter (DSC).

7. Powdered material (M) according to any of claims 1 to 6, wherein the flow aid (F) is an inorganic pigment selected from the group consisting of silicon dioxide, aluminum oxide and titanium oxide.

8. Powdered material (M) according to any of claims 1 to 7, wherein the glidant (F) is fumed silica.

9. The powdery material (M) according to any of claims 1 to 7, wherein the material (M) has a d ranging between 15 and 80 μ M measured by laser light scattering in isopropanol_0.5The value is obtained.

10. A method for fabricating a three-dimensional (3D) article, part, or composite, comprising:

a) depositing successive layers of powdery material (M) according to any one of claims 1 to 9, and

b) printing a layer prior to depositing the subsequent layer.

11. The method of claim 10, wherein step b) comprises selectively sintering the powder via electromagnetic radiation.

12. A three-dimensional (3D) article, part or composite material obtainable by additive manufacturing of the powdered material (M) according to any one of claims 1-9, preferably Selective Laser Sintering (SLS), composite-based additive manufacturing technology ("CBAM") or multi-jet Melting (MJF).

13. Use of the powdered material (M) according to any one of claims 1-9 for manufacturing a three-dimensional (3D) object using additive manufacturing, preferably Selective Laser Sintering (SLS), composite material based additive manufacturing technology ("CBAM") or multi jet Melting (MJF).

14. Use of a polymer component (P) comprising at least one poly (arylene sulfide) (PAS) polymer comprising recurring units P, q and r according to formula (I):

wherein

n_p、n_qAnd n_rMole% of each repeating unit p, q, and r, respectively;

the repeating units p, q and r are arranged in a block manner, in an alternating manner or randomly;

2％≤(n_q+n_r)/(n_p+n_q+n_r)≤9％；n_qis not less than 0% and n_rIs more than or equal to 0 percent;

j is zero or an integer varying between 1 and 4;

R¹selected from the group consisting of: halogen atom, C₁-C₁₂Alkyl radical, C₇-C₂₄Alkylaryl group, C₇-C₂₄Aralkyl radical, C₆-C₂₄Arylene radical, C₁-C₁₂Alkoxy, and C₆-C₁₈An aryloxy group which is a group having a lower alkoxy group,

optionally in combination with one or more glidants (F) and/or one or more additives (A),

the powdered material (M) is used for additive manufacturing, preferably Selective Laser Sintering (SLS), composite material based additive manufacturing technology ("CBAM") or multi jet Melting (MJF).

15. Use of the article, part, or composite of claim 12 in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer products.

Technical Field

The present invention relates to a powdered material (M) comprising at least one poly (arylene sulfide) (PAS) polymer, and to a process for manufacturing a three-dimensional (3D) article, part or composite from such a powdered material (M). The invention also relates to 3D articles, parts or composites obtainable from such a method, and the use of said articles, parts or composites in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer products.

Background

Many objects, from everyday items to automotive parts, are made from a single piece of material, or are milled or carved from a larger piece of material. An alternative method of manufacturing an object is to deposit a thin layer of material, such as a powder, and then add another layer on top, then add another layer and another layer, and so on. This method of addition is known as Additive Manufacturing (AM), more commonly referred to as 3D printing. The range of specifically designed 3D printed products currently on the market is quite wide, from automotive parts to dental implants. Notably they can be manufactured using plastic. It is expected that additive manufacturing will break established practices and subvert the conventional assumptions about mass production in remote plants. Local manufacturing of small batches, or even individual products, close to the end user will become feasible.

One of the fundamental limitations associated with known AM methods using polymeric part materials in powder form is based on the lack of identification of materials that exhibit the correct set of properties to be able to print out 3D parts/objects with acceptable density and mechanical properties.

Poly (arylene sulfide) (PAS) polymers are semi-crystalline thermoplastic polymers with significant mechanical properties, such as high tensile modulus and high tensile strength, as well as significant stability to thermal degradation and chemical reactivity. They are also characterized by excellent melt processability, such as injection molding.

This broad range of properties makes PAS polymers suitable for a number of applications, such as the automotive, electrical, electronic, aerospace, and appliance markets.

Despite the above advantages, PAS polymers are known to have low impact resistance and low elongation at break, in other words, poor ductility and poor toughness.

Accordingly, there is a need for a PAS polymer for additive manufacturing having improved ductility and toughness while maintaining high tensile strength.

WO 2017/1226484 (Toray) describes the use of PAS resin as powder for producing 3D models by powder sintering through a 3D printer.

WO 2020/011991 (Solvay) relates to a PAS polymer which can be used in AM. The PAS was such that it exhibited, as a main technical feature, a calcium content of less than 200ppm as measured by X-ray fluorescence (XRF) analysis calibrated with standards via ICP-OES.

WO 2020/011990 (solvay) describes PAS polymers that exhibit flowability, which makes the powder well suited for use in applications such as the manufacture of 3D objects using laser sintering based AM systems, where the powder must exhibit good flow behavior in order to build up powder during the printing process.

These documents do not describe powdered materials for AM comprising PAS polymers as described herein. The use of such materials shows better printing characteristics and improved final part properties (mechanical and part aesthetics) compared to the powders of the prior art.

Disclosure of Invention

Disclosed herein is a powdered material (M), and a method of manufacturing a 3D object (i.e. an article, part or composite) from such powdered material (M) comprising at least one poly (arylene sulfide) polymer (also referred to herein as "poly (arylene sulfide)" or PAS). Reference to poly (arylene sulfide) polymers specifically includes, but is not limited to, polyphenylene sulfide polymers, also referred to herein as "polyphenylene sulfide" or PPS.

The powdery material (M) of the present invention may have a regular shape such as a spherical shape, or a complex shape obtained by grinding/milling the polymer component (P) in the form of pellets or a coarse powder (i.e., at least PAS polymer).

In the present specification, the following terms have the following meanings, unless otherwise specified.

The expression "sulphide moiety" is intended to denote the-S-bridge of the repeating unit p in formula (I).

The expression "sulfoxide moiety" is intended to denote the-SO-bridge of the repeating unit q in formula (I).

The expression "sulfone moiety" is intended to denote the-SO of the repeating unit r in formula (I)₂-a bridge.

The expression "oxidized moiety" is more general and is intended to mean both a sulfoxide moiety and a sulfone moiety.

In the present application:

even if any description described in relation to a specific embodiment is applicable to and interchangeable with other embodiments of the present disclosure;

-when an element or component is said to be comprised in and/or selected from a list of recited elements or components, it is to be understood that in the relevant examples explicitly contemplated herein, the element or component may also be any one of the individual elements or components recited therein, or may also be selected from a group consisting of any two or more of the explicitly recited elements or components; any element or component listed in a list of elements or components can be omitted from this list; and is

Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within that range and the endpoints and equivalents of that range.

In a first aspect, the present invention relates to a powdered material (M) comprising a poly (arylene sulfide) (PAS) polymer comprising recurring units p, q, and r according to formula (I):

wherein

n_p、n_qAnd n_rMole% of each repeating unit p, q, and r, respectively;

the repeating units p, q and r are arranged in a block manner, in an alternating manner or randomly;

2％≤(n_q+n_r)/(n_p+n_q+n_r)≤9％；

n_qis not less than 0% and n_rIs more than or equal to 0 percent;

j is zero or an integer varying between 1 and 4;

R¹selected from the group consisting of: halogen atom, C₁-C₁₂Alkyl radical, C₇-C₂₄Alkylaryl group, C₇-C₂₄Aralkyl radical, C₆-C₂₄Arylene radical, C₁-C₁₂Alkoxy, and C₆-C₁₈An aryloxy group.

Powdery material (M)

The pulverulent material (M) according to the invention comprises at least one polymer component (P). The polymer component (P) of the powdery material (M) may comprise one or more PAS as described below. It may also comprise at least one additional polymeric material, i.e., at least one polymer or copolymer different from the PAS polymers described herein. Such additional polymeric materials may for example be selected from the group consisting of: poly (aryl ether sulfone) (PAES) polymers such as poly (biphenyl ether sulfone) (PPSU) polymers or Polysulfone (PSU) polymers, and poly (aryl ether ketone) (PAEK) polymers such as poly (ether ketone) (PEEK) polymers. This additional polymeric material may also be a poly (arylene sulfide) (PAS) other than PAS described herein, such as a homopolymer of poly (phenylene sulfide) (PPS) polymer.

The PAS described herein comprises repeating units p, q, and r according to formula (I):

wherein the repeating units p, q and r are arranged in a block manner, in an alternating manner or randomly.

In formula (I), j is zero or an integer varying between 1 and 4.

Preferably, j in formula (I) is zero, which means that the aromatic ring is unsubstituted. Thus, the repeating units p, q and r are according to the following formulae (II), (III) and (IV), respectively:

when j varies between 1 and 4, R¹May be selected from the group consisting of: halogen atom, C₁-C₁₂Alkyl radical, C₇-C₂₄Alkylaryl group, C₇-C₂₄Aralkyl radical, C₆-C₂₄Arylene radical, C₁-C₁₂Alkoxy, and C₆-C₁₈An aryloxy group.

The molar percentages of the repeating units p, q and r in formula (I) (each designated as n)_p、n_qAnd n_r) Is made to be less than or equal to 2 percent (n)_q+n_r)/(n_p+n_q+n_r)≦ 9%, which means that the PAS polymer having formula (I) comprises between 2 and 9 mol.% of oxidized repeat units q and r, based on the total number of repeat units p, q, and r in the polymer.

The PAS polymer described herein comprises repeating unit p, and it comprises repeating units q and/or r. When the PAS polymer contains repeating units p, q and r, n in the above equation_qAnd n_rAre all made of>0 percent. Alternatively, the PAS polymer described herein may comprise repeating units p and q, but no repeating unit r. In this case, n_qIs not less than 2%, but n_r0%. According to a third possibility, the PAS polymer described herein may comprise repeating units p and r, but no repeating unit q. In this case, n_rIs not less than 2%, but n_q＝0％。

In some embodiments, the mole percentages of repeating units p, q, and r in formula (I) are such that:

2.2％≤(n_q+n_r)/(n_p+n_q+n_r)less than or equal to 8.8 percent or

2.5％≤(n_q+n_r)/(n_p+n_q+n_r)Less than or equal to 8.5 percent or

2.8％≤(n_q+n_r)/(n_p+n_q+n_r)Less than or equal to 8.2 percent or

3.0％≤(n_q+n_r)/(n_p+n_q+n_r)≤7.0％

According to the factExamples n_p+n_q+n_rIs at least 50%, meaning that the PAS comprises at least 50 mol.% of repeating units p, q, and r, based on the total moles of repeating units in the PAS polymer. For example, n is based on the total moles of repeating units in the PAS polymer_p+n_q+n_rThe sum of (a) may be at least 60%, at least 70%, at least 80%, at least 90% or even at least 95%.

According to embodiments described herein, PAS consists of, or consists essentially of, repeat unit p, and repeat units q and/or r. The expression "consisting essentially of" means that the PAS comprises recurring units p, and recurring units q and/or r, and less than 10 mol.%, preferably less than 5 mol.%, more preferably less than 3 mol.%, even more preferably less than 1 mol.% of other recurring units different from recurring units p, q, and r, based on the total moles of recurring units in the PAS polymer.

According to an embodiment, the PAS polymer described herein further comprises recurring units s and/or t having the formulae (V) and/or (VI), respectively:

wherein:

i is zero or an integer varying between 1 and 4;

R²selected from the group consisting of: halogen atom, C₁-C₁₂Alkyl radical, C₇-C₂₄Alkylaryl group, C₇-C₂₄Aralkyl radical, C₆-C₂₄Arylene radical, C₁-C₁₂Alkoxy, and C₆-C₁₈An aryloxy group.

In formulae (V) and (VI), i is preferably zero, meaning that the aromatic ring is unsubstituted.

N is based on the total number of moles of repeating units in the PAS polymer_s+n_tLess than 10 mol.%, preferably less than 5 mol.%, more preferably less than 3 mol.%, even more preferably less than 1 mol.%.

According to an embodiment, n_p+n_q+n_rIs 100%, where n_qAnd n_rAt least one of>0mol.％。

According to an embodiment, n_p+n_q+n_rThe sum of (a) is less than 100%. In this embodiment, the PAS polymer comprises at least one repeating unit different from p, r, and q, e.g., a repeating unit according to formula (V) and/or (VI).

According to another embodiment, n_p+n_q+n_r+n_s+n_tIs 100%, where n_qAnd n_rAt least one of>0 mol.%, and n_sAnd n_tAt least one of>0mol.％。

Preferably, the PAS has a melt flow rate (according to ASTM D1238, procedure B, at 315.6 ℃ C. under a weight of 1.27 kg) of at most 700g/10min, more preferably at most 500g/10min, even more preferably at most 200g/10min, still more preferably at most 50g/10min, yet more preferably at most 35g/10 min.

Preferably, the PAS has a melt flow rate (according to ASTM D1238, procedure B, at 315.6 ℃ C. under a weight of 1.27 kg) of at least 1g/10min, more preferably at least 5g/10min, even more preferably at least 10g/10min, still more preferably at least 15g/10 min.

Preferably, the PAS has a melting point of at least 240 ℃, more preferably at least 248 ℃, even more preferably at least 250 ℃ when determined in a Differential Scanning Calorimeter (DSC) in the 2 nd thermal scan according to ASTM D3418 using a heating and cooling rate of 20 ℃/min.

Preferably, the PAS has a melting point of at most 280 ℃, more preferably at most 278 ℃, even more preferably at most 275 ℃ as determined according to ASTM D3418 using a heating and cooling rate of 20 ℃/min in the 2 nd thermal scan in a Differential Scanning Calorimeter (DSC).

In some embodiments, PAS has a heat of fusion greater than 20J/g, preferably greater than 21J/g or greater than 22J/g, as determined in the 2 nd thermal scan in a Differential Scanning Calorimeter (DSC) using a heating and cooling rate of 20 ℃/min according to ASTM D3418.

The powdery material (M) of the present invention comprises a polymer component (P) comprising at least one PAS polymer as described above. The powdery material (M) of the present invention may consist essentially of one or several polymers, e.g. may consist essentially of one of the PAS polymers described herein, or may further comprise additional components, e.g. flow aids/agents (F), as described below and/or one or several additives (a). When the powdery materials (M) of the present invention comprise additional components, they may be added or blended with the polymer components described herein before, during or after the milling step.

In some embodiments of the invention, the powdered material (M) has a d of less than 150 μ M as measured by laser light scattering in isopropanol₉₀The value is obtained. According to an embodiment, the powdered material (M) has a d of less than 120 μ M, preferably less than 110 μ M or less than 100 μ M as measured by laser light scattering in isopropanol₉₀The value is obtained.

In some embodiments of the invention, the powdered material (M) has a d higher than 0.1 μ M as measured by laser light scattering in isopropanol₁₀The value is obtained. According to a preferred embodiment, the powdered material (M) has a d of more than 1 μ M, preferably more than 5 μ M or more than 10 μ M as measured by laser light scattering in isopropanol₁₀The value is obtained.

In some embodiments of the invention, the powdered material (M) has a d as measured by laser light scattering in isopropanol₅₀The value is between 40 μm and 70 μm, preferably between 40 μm and 60 μm, or between 43 μm and 58 μm, or between 45 μm and 55 μm. A powdered material (M) with such a particle size distribution is for example very suitable for Selective Laser Sintering (SLS).

In some embodiments of the invention, the powdered material (M) has a d of less than 195 μ M as measured by laser light scattering in isopropanol₉₉The value is obtained. According to a preferred embodiment, the powdered material (M) has a d of less than 190 μ M, preferably less than 180 μ M or less than 170 μ M as measured by laser light scattering in isopropanol₉₉The value is obtained.

The powdery material (M) of the invention may have a soaking/emptying temperature ranging from 0 to 30M, as measured by ISO 9277 using up to 25 ℃²Per g, youIs selected from 0.5 to 20m²G, more preferably from 0.8 to 15m²BET surface area in g.

The powdery material (M) of the present invention may have a bulk density (or poured bulk density) of at least 0.35, preferably at least 0.45, most preferably at least 0.50. Bulk density is at most 5.

According to one embodiment, the powdered material (M) of the present invention comprises at least 50 wt.% of the polymer component (P), for example at least 60 wt.% of the polymer component (P), at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 98 wt.%, or at least 99 wt.% of the polymer component (P) described herein, based on the total weight of the powdered material (M).

According to one embodiment, the polymer component (P) comprises at least 50 wt.% of PAS as described herein, such as at least 60 wt.% of PAS as described herein, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 98 wt.%, or at least 99 wt.% of PAS as described herein, based on the total weight of the powder.

Before using the powder for additive manufacturing, additional components may notably be added to the polymer component (P) before, during or after the milling step of the polymer component (P), notably the milling step of PAS as described herein. For example, the additional component may be a glidant (F). This glidant (F) may, for example, be hydrophilic. Examples of hydrophilic flow aids are inorganic pigments notably selected from the group consisting of silica, alumina and titania. Fumed silica may be mentioned. Fumed silica is available under the trade name(winning companies (Evonik)) and(Cabot corporation) are commercially available. Fumed alumina is known under the trade name(Cabot corporation) commercially available.

In one embodiment of the invention, the powdered material (M) comprises from 0.01 to 10 wt.% of the flow aid (F), for example from 0.05 to 8 wt.%, from 0.1 to 6 wt.% or from 0.15 to 5 wt.% of at least one flow aid (F), such as at least fumed silica or fumed alumina, based on the total weight of the powder.

These silicas or aluminas are composed of primary particles of nanometric dimensions (typically between 5 and 50nm for fumed silicas or aluminas). These primary particles combine to form aggregates. When used as a glidant, silicon dioxide or aluminum oxide is found in various forms (primary particles and aggregates).

The powdery material (M) of the present invention may further comprise, for example, one or several additives (a) selected from the group consisting of: fillers (e.g., carbon fibers, glass fibers, milled carbon fibers, milled glass fibers, glass beads, glass microspheres, wollastonite, silica beads, talc, calcium carbonate), colorants, dyes, pigments, lubricants, plasticizers, flame retardants (e.g., halogen and non-halogen containing flame retardants), nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, and electromagnetic absorbers. Specific examples of these optional additives (a) are titanium dioxide, zinc oxide, cerium oxide, silicon dioxide or zinc sulphide, glass fibres, carbon fibres.

The powdery material (M) of the present invention may further contain a flame retardant such as a halogen and a halogen-free flame retardant.

In another embodiment of the invention, the powdered material (M) comprises from 0.01 to 30 wt.% of the at least one additive (a), for example from 0.05 to 25 wt.%, from 0.1 to 20 wt.% or from 0.15 to 10 wt.%, based on the total weight of the powder.

According to one embodiment, the powdered material (M) of the invention comprises:

-at least 50 wt.% of a polymer component (P),

-from 0.01 to 10 wt.%, from 0.05 to 8 wt.%, from 0.1 to 6 wt.% or from 0.15 to 5 wt.% of at least one glidant (F), and

-optionally at least one additive (a), for example selected from the group consisting of: fillers (e.g., carbon fibers, glass fibers, milled carbon fibers, milled glass fibers, glass beads, glass microspheres, wollastonite, silica beads, talc, calcium carbonate) colorants, dyes, pigments, lubricants, plasticizers, flame retardants (e.g., halogen and halogen-free flame retardants), nucleating agents, heat stabilizers, light stabilizers, antioxidants, processing aids, fluxes, and electromagnetic absorbers,

% is based on the total weight of the powder.

The PAS polymers described herein can be prepared by the following method: the method comprises the step of oxidizing solid particles of poly (arylene sulfide) (PAS-p) having the formula (VII):

wherein:

j is zero or an integer varying between 1 and 4;

R¹selected from the group consisting of: halogen atom, C₁-C₁₂Alkyl radical, C₇-C₂₄Alkylaryl group, C₇-C₂₄Aralkyl radical, C₆-C₂₄Arylene radical, C₁-C₁₂Alkoxy, and C₆-C₁₈An aryloxy group which is a group having a lower alkoxy group,

wherein the oxidizing step occurs in a liquid containing an oxidizing agent.

The oxidizing agent is used in an amount such that from 2 to 9 mol.% of the sulfide moieties of PAS-p are oxidized to sulfoxide moieties and/or sulfone moieties, thus providing PAS as described above. The liquid advantageously comprises an oxidizing agent in an amount of from 2 to 9 mol.% of the sulfide fraction in the PAS-p polymer. The liquid may for example comprise acetic acid. The oxidizing agent may be, for example, hydrogen peroxide. For example, the liquid may also comprise a peracid formed from the reaction of acetic acid with hydrogen peroxide.

The invention also relates to a method for producing a powdery material (M) for a layer-by-layer production method for three-dimensional parts, wherein the fine powder is produced by grinding, solvent precipitation, melt spraying or spray drying of coarse powders or granules.

The powdered material (M) used in the additive manufacturing method of the present invention may be obtained by:

step 1') grinding the polymer component (P), notably the PAS polymer described herein; and

step 2 ') the polymer component (P) from step 1') is blended with optional components, for example at least one glidant (F).

The powdered material (M) used in the additive manufacturing method of the invention may alternatively be obtained by:

step 1') blending the polymer component (P) with optional components, e.g. at least one glidant (F), and

step 2 ") milling the blend from step 1"), notably the PAS polymer described herein.

The grinding step can be carried out in a pin-pan mill, a jet mill with classifier/fluidized jet mill, an impact mill plus classifier, a pin/pin beater mill or a wet grinding mill or a combination of these devices.

The ground powdered material may preferably be separated or screened in an air separator or classifier to obtain a predetermined fractionation spectrum (fraction spectrum). The powdery material (M) is preferably screened before use in a printer. Screening includes removing particles greater than 200 μm, greater than 150 μm, greater than 140 μm, 130 μm, 120 μm, 110 μm, or greater than 100 μm using suitable equipment.

According to another aspect, the invention relates to a method for manufacturing a three-dimensional (3D) article, part or composite material, comprising depositing successive layers of a powdery material (M) and selectively sintering each layer before depositing a subsequent layer, for example by subjecting the powder to electromagnetic radiation.

The additive manufacturing method of the invention is preferably selected from the group consisting of Selective Laser Sintering (SLS), composite-based additive manufacturing technology ("CBAM"), or multi-jet Melting (MJF).

Additive manufacturing methods are typically performed using a 3D printer.

For example, an SLS 3D printer is available under the trade name EOS from EOS Corporation (EOS Corporation)P is available.

For example, the MJF 3D printer is available from Hewlett-Packard Company under the trade name Multi Jet Fusion.

The powder may also be used to produce continuous fiber composites in a CBAM process, such as developed by the company implantable Objects.

According to an embodiment, the step of printing the layer comprises selective sintering of the powdered material (M) by subjecting the powdered material (M) to electromagnetic radiation (e.g. a high power laser source such as an electromagnetic beam source).

A 3D object/article/part can be built on a substrate (e.g., a horizontal substrate and/or a planar substrate). The base may be movable in all directions (e.g., in a horizontal or vertical direction). During the 3D printing process, the substrate may for example be lowered in order to sinter successive layers of unsintered polymer material on top of a previous layer of sintered polymer material.

According to an embodiment, the method further comprises the step of producing the support structure. According to this embodiment, the 3D object is built on a support structure and both the support structure and the 3D object are produced using the same AM method. The support structure may be used in a variety of situations. For example, the support structure may be used to provide sufficient support for a printed or printing object to avoid deformation of the formed 3D object, especially when the 3D object is not planar. This is especially true when the temperature used to maintain the printed or printing 3D object is below the resolidification temperature of the polymer component (e.g., PAS polymer).

The 3D printer may include a sintering chamber and a powder bed, both maintained at certain specific temperatures.

The powdered material (M) to be printed can be preheated to a processing temperature (Tp) higher than the glass transition temperature (Tg) and lower than the melting temperature (Tm) of the powder. The preheating of the powdered material (M) makes it easier for the laser to raise the temperature of selected areas of the unfused powder layer to the melting point. The laser causes fusion of the material only at the location specified by the input information. The laser energy exposure is typically selected based on the polymer used and to avoid polymer degradation.

The inventors have realized that the printing of the powdery material (M) of the invention comprising modified PAS can be performed at a processing temperature (Tp) lower than the processing temperature of the powdery material (M) comprising unmodified PAS. This is advantageous because it has a positive effect on energy consumption.

Articles and uses

The present invention also relates to articles, parts or composites comprising the poly (arylene sulfide) (PAS) described herein obtainable by the additive manufacturing process of the present invention, and the use of the articles, parts or composites in oil and gas applications, automotive applications, electrical and electronic applications, or aerospace and consumer products.

For automotive applications, the article may be a bottom shell (e.g., oil pan), a panel (e.g., exterior body panel including, but not limited to, rear side panel, trunk, hood; and interior body panel including, but not limited to, door panel and instrument panel), side panel, rearview mirror, bumper, bar (e.g., torsion bar and rocker bar), rod (rod), suspension component (e.g., suspension rod, leaf spring, suspension arm), and turbocharger component (e.g., housing, volute, compressor wheel, and impeller), tubing (for transporting, for example, fuel, coolant, air, brake fluid). For oil and gas applications, the article of manufacture may be a drilling component, such as a downhole drill pipe, a chemical injection pipe, a subsea umbilical (umbilical), and a hydraulic control line. The article may also be a mobile electronic device component.

According to an embodiment, the composite material obtainable from the additive manufacturing method of the invention is a continuous fiber reinforced thermoplastic composite material. The fibers may be comprised of carbon, glass, or organic fibers such as aramid fibers.

The invention also relates to the use of the powdered material (M) described herein for manufacturing a three-dimensional (3D) object using additive manufacturing, preferably Selective Laser Sintering (SLS), composite material based additive manufacturing technology ("CBAM") or multi jet Melting (MJF).

The invention also relates to the use of a polymer component (P) comprising at least one poly (arylene sulfide) (PAS) polymer as described above for the manufacture of a powdered material (M) for additive manufacturing, preferably Selective Laser Sintering (SLS), composite-based additive manufacturing technology ("CBAM") or Multi Jet Fusion (MJF).

The invention will now be described with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention.

Experimental part

Material

QA200N is a poly (phenylene sulfide) commercially available from Solvay Specialty Polymers USA.

A30% w/w aqueous solution of hydrogen peroxide was purchased from Fischer (Fischer).

Acetic acid of 99% purity was purchased from VWR.

Synthesis examples

PAS Polymer #1 (inventive)

Under nitrogen atmosphereQA200N (200g, 1.0 eq) was suspended in acetic acid (400mL) in a 1L reactor equipped with an inclined four-corner stirrer, a condenser, a double jacket for heating and a syringe pump.

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

The temperature was raised to 70 ℃ (jacket set at 75 ℃) and the reaction mixture was stirred at that temperature for 3 hours. The stirring speed was set to 300 rpm. The supernatant was then analyzed using a Quantofix peroxide test bar to confirm the absence of peroxide.

The reaction mixture was then cooled to room temperature and filtered.

The recovered solid was washed twice with acetic acid at room temperature (2 × 100 mL). The solid is then dried in a rotary evaporator at a pressure of 20mbar and a temperature of 50 ℃ for 2 hours. The recovered solid was then dried under vacuum (about 20mbar) at 120 ℃ for 7 hours.

The resulting product is a poly (phenylene sulfide) having the formula (I) wherein j ═ 0, n_p＝96％、n_q+n_r4% of the total weight. Therefore, under these conditions,the 4 mol.% sulfide moiety of QA200N was oxidized to sulfoxide and sulfone moieties.

Characterization of the Polymer component

DSC/Heat of fusion

DSC analysis was performed according to ASTM D3418 on a DSC Q200-5293 TA instrument and data was collected by a two-hot-one-cold method. The protocol used was as follows: 1 st heating cycle: from 30.00 ℃ to 350.00 ℃ at 20.00 ℃/min; isothermal hold for 5 minutes; 1 st cooling cycle: from 350.00 ℃ to 30.00 ℃ at 20.00 ℃/min; heating cycle 2: from 30.00 ℃ to 350.00 ℃ at 20.00 ℃/min. The melting temperature (T) was recorded during the 1 st and 2 nd heating cycles_m) The melt crystallization temperature (T) is recorded during the cooling period_mc) The glass transition temperature (T) is recorded during the 2 nd heating cycle_g) And the enthalpy of fusion (Δ H) is recorded during the 2 nd heating cycle.

Preparation of a ground-powder Material of the Polymer component

Will be provided withQA200N (comparative) and PAS Polymer #1 (invention) were prepared by grinding in a rotor mill (Retsch)Rotor Mill SR300) was milled to powder and characterized. The results are presented in table 1.

The powder was then mixed with 0.3% fumed silica (from cabot corporation) by rollerM-5) and sieved through a 120 mesh draw bolt cloth (147 μ M pore size).

PSD

The particle size of the final powder (d) was determined by laser scattering technique on a Microtrac S3500 analyzer in wet mode (128 channels between 0.0215 and 1408 μm) with 3 mean runs₁₀、d₅₀And d₉₀). The solvent used was isopropanol with a refractive index of 1.38 and the particles were assumed to have a refractive index of 1.59. The ultrasonic mode (25W/60 sec) was activated and the flow rate was set to 55%. The results are presented in table 2 below.

BET surface area and bulk Density

The BET surface area (multi-point) of the final powder was determined by nitrogen (N2) adsorption on a TriStar II Plus version 3.01 surface area and pore analyser according to ISO 9277. The bulk density of the powder was determined by method a of ASTM D1895. The results are presented in table 2 below.

TABLE 1

TABLE 2

Printing

In thatThe P800 SLS printer prints with the following print settings: 17 watt profile (hatch) laser power, 8.5 watt profile laser powerRate, laser speed of 2.65m/s, and cooling rate after printing is completed of less than 10 deg.C/min.

The powdered material was sintered into ASTM type I tensile bars.

Characterization of the stretched strips

ASTM type I tensile bars were tested according to ASTM D638, with the results reported in table 3 being the average from 5 bars.

Results

TABLE 3

Will contain unmodified PPSThe powder of QA200N (comparative powder) was first printed at a processing temperature of 263 ℃, but this resulted in curling. Therefore, the processing temperature of the comparative powder was adjusted to 275 ℃ to avoid curling. The powder based on PAS polymer #1 of the present invention was printed at a processing temperature of 263 ℃ and no curling occurred.

The inventive powder shows better printing characteristics and resulting printed part properties (mechanical and part aesthetics) compared to the comparative powder. During the printing process, the powder of the invention exhibits a smooth bed surface throughout the printing process. This is critical to achieving a stable print which will result in successful completion of the print and acceptable parts.

The strips printed with the powder of the invention present a smooth surface.

The use of the powder according to the invention results in mechanical properties (both ultimate tensile strength and tensile elongation at break) of the parts superior to those of the unmodified oneQA200N。