• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a composition comprising from 99.6 to 99.99% by weight of at least one powder of at least one polyarylene ether ketone and 0.01 to 0.4% by weight of a hydrophilic flow agent. This hydrophilic flow agent is characterized by a weight gain (amount of water absorbed) after 5 days of conditioning at a relative humidity of 95% greater than 0.5%. This mass uptake of the flow agent is determined by Karl Fisher measurement after desorption of water by a 15 min treatment at 170 ° C. This composition is suitable for laser sintering. In particular, it allows an excellent compromise flowability and coalescence of the powder.
    公开号:FR3015506A1
    申请号:FR1363201
    申请日:2013-12-20
    公开日:2015-06-26
    发明作者:Benoit Brule；Herve Ster；Cyrille Mathieu；Nadine Decraemer
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a composition comprising from 99.6 to 99.99% by weight of at least one powder of at least one poly-arylene-ether-ketone-ketones allowing an excellent compromise flowability and coalescence suitable for laser sintering. -arylene-ether-ketone and 0.01 to 0.4% by weight of a hydrophilic flow agent. This hydrophilic flow agent is characterized by a weight gain (amount of water absorbed) after 5 days of conditioning at a relative humidity of 95% greater than 0.5%. This mass uptake of the flow agent is determined by Karl Fisher measurement after desorption of water by a 15 min treatment at 170 ° C. This composition is suitable for laser sintering. In particular, it allows an excellent compromise flowability and coalescence of the powder. Polyarylene ether ketones and more particularly polyether ketone ketones (PEKK) are very effective materials. They are used for demanding applications in temperature and / or in mechanical or even chemical stresses. These polymers are found in fields as varied as aeronautics, offshore drilling, medical implants. They can be implemented by molding, extrusion, compression, spinning or laser sintering in particular. However, their implementation in the latter process requires powder preparation conditions ensuring good flowability for implementation in the laser sintering process as described below. The technology for sintering powders under a laser beam is used to manufacture three-dimensional objects such as prototypes, models, but also functional parts, in particular in the automotive, nautical, aeronautical, aerospace, medical ( prostheses, auditory systems, cellular tissues ...), textiles, clothing, fashion, decoration, housings for electronics, telephony, home automation, computer science, lighting. A thin layer of powder is deposited on a horizontal plate held in a chamber heated to a certain temperature. The laser provides the energy necessary to sinter the powder particles at different points of the powder layer according to a geometry corresponding to the object, for example using a computer having in memory the shape of the object. and restoring the latter in the form of slices. Then, the horizontal plate is lowered by a value corresponding to the thickness of a layer of powder (for example between 0.05 and 2 mm and generally of the order of 0.1 mm) and then a new layer is deposited. powder layer. The laser provides the energy necessary to sinter the powder particles to a geometry corresponding to this new slice of the object and so on. The procedure is repeated until the whole object has been made. In this method of sintering powders under a laser beam, it is imperative to have powders which have good flowability, which allows a good layering of said powders. On the other hand, good coalescence of the powder is necessary after the laser-induced fusion, so that the mechanical properties of the artifacts are maximized. Thus, powders having a good flowability and good coalescence during the sintering process are sought. In the field of laser sintering, it is customary to add flow agents to improve the flowability of the powders. US 2004/0204531 describes the interest in the polyamide of hydrophobic silicas versus hydrophilic silicas. Indeed, the flowability is deteriorated after moisture recovery in the case of the use of hydrophilic silicas while it is unchanged in the case of the use of hydrophobic silicas. In the field of polyarylene ether ketones (PAEK), the flowability is known to be improved by using a suitable heat treatment. U57847057 relates to a method for thermal treatment of polyarylene ether ketone powders by exposing the powder to a heat treatment greater than 30 minutes at a temperature of 20 ° C above the glass transition temperature of the polymer. This treatment applied to polyether-ether-ketones (PEEK) makes it possible to obtain acceptable flowable powders for the laser sintering process. The coalescence aspect is not discussed in this patent, in particular no example demonstrates that the coalescence is effective, modified or even improved by the heat treatment. No. WO2012047613 also describes a heat treatment applied more particularly to polyketherketone ketone (PEKK) powders consisting in exposing the powder to a heat treatment lasting several hours between the transition temperatures of the different crystalline phases, more particularly as it approaches the melting temperature of the polymer, corresponding to the crystalline form having the transition at the highest temperature. The flowability of the powder is improved and the resulting crystallinity of this treatment is preserved during the sintering process, giving the sintered object some advantageous physical properties, but appearing insufficient for certain applications. The coalescence aspect is not discussed in this patent, in particular no example demonstrates that the coalescence is effective, modified or even improved by the heat treatment. To meet the need for powders having good flowability and good coalescence, the Applicant has conducted a series of tests showing that for the poly-arylene-ether-ketones, the addition of hydrophilic flow agent allows on the one hand, good flowability and on the other hand, this flowability is retained even after a stay in a humid atmosphere. This last result appears unexpected and very surprising in view of the prior art (US 2004/0204531). In addition, the Applicant has found that for such compositions, the coalescence of these hydrophilic flow-agent-added polyarylene-ether-ketone powders is greater than that of poly-5-arylene-ether-ketone powders with added viscosity. hydrophobic flow agent. SUMMARY OF THE INVENTION The invention relates to a composition comprising from 99.6 to 99.99% by weight of at least one powder of at least one polyarylene ether ketone and 0.01 to 0.4% by weight of a hydrophilic flow, preferably from 0.01 to 0.2% by weight of a hydrophilic flow agent and, more preferably, from 0.01 to 0.1% by weight of a hydrophilic flow agent. This hydrophilic flow agent is characterized by a weight gain (amount of water absorbed) after 5 days of conditioning at a relative humidity of 95% greater than 0.5%, preferably greater than 0.8%. This mass uptake of the flow agent is determined by Karl Fisher measurement after desorption of water by a 15 min treatment at 170 ° C.
    [0002] The invention also relates to the use of the compositions of the invention as well as the objects manufactured using these compositions, in particular using a laser sintering method.
    [0003] Detailed Description: The polyarylene ether ketones (PAEKs) used in the invention comprise the units of the following formulas: (-Ar-X-) and (-Ari-Y-) in which: -6- Ar and Art each denotes a divalent aromatic radical; A minority (<10%) of these units can be replaced by radicals of valence greater than 2 to introduce branching. Ar and Art may be chosen, preferably, from 1,3-phenylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2,6 naphthylene; X denotes an electron-withdrawing group; it can be chosen, preferably, from the carbonyl group and the sulphonyl group, Y denotes a group chosen from an oxygen atom, a sulfur atom, an alkylene group, such as -CH 2 - and isopropylidene. In these units X and Y, at least 50%, preferably at least 70% and more particularly, at least 80% of the X groups are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least at least 80% of the Y groups represent an oxygen atom. According to a preferred embodiment, 100% of the X groups denote a carbonyl group and 100% of the Y groups represent an oxygen atom.
    [0004] More preferentially, the polyarylene ether ketone (PAEK) may be chosen from: a polyetheretherketone also called PEEK comprising units of formula I: Formula I-7 Combinations may be totally para (Formula I), but it would not be outside the scope of the invention to introduce, partially or totally, meta sequences. Two examples (non-limiting list) are provided below: Or else: a polyether ketone also called PEK, comprising units of formula II: Formula II Similarly, the sequences may be totally para (Formula II ) but it would not depart from the scope of the invention by introducing, partially or completely, meta-8 or -a polyether ketone-ketone sequences also called PEKK, comprising units of formula IIIA, formula IIIB and their mixture: Formula IIIA 0 Formula IIIB15 -9- and a polyether-ether-ketone-ketone also called PEEKK, comprising units of formulas IV: Formula IV In the same way it is possible to introduce meta linkages in this structure without leaving of the invention. Other arrangements of the carbonyl group and the oxygen atom are also possible. It would not depart from the scope of the invention by their use. It is also possible to incorporate into the structure a divalent phthalazinone radical of the following formula: The polyarylene ether ketone that can be used according to the invention can be semi-crystalline or amorphous. Preferably, the polyarylene ether ketones are polyetherketone ketones comprising a mixture of the units IIIA and IIIB so that the weight percentage in terephthalic unit with respect to the sum of the terephthalic and isophthalic units is between 55% and 85% and preferably between 55% and 70%, ideally 60%. By terephthalic and isophthalic unit is meant the formula of terephthalic and isophthalic acids respectively. These polyarylene ether ketones are in the form of powders which may have been prepared by grinding or precipitation. In the context of the invention, mixtures of different polyarylene ether-ketone powders are not excluded. According to one preference, the mixtures of different polyarylene ether ketone powders comprise a polyether ketone ketone combined with another polyarylene etherketone or a mixture of two PEKKs of different chemical structure. Thus, a polyarylene-ether-ketone will be associated with PEK, PEEKEK, PEEK, PEKEKK, PEKK. According to one preferred form, PEKK will be associated with PEK, PEEKEK, PEEK, PEKEKK or a PEKK of different chemical formula, the PEKK representing more than 50% by mass, including the limit. The hydrophilic flow agents used in the context of the invention may be inorganic pigments preferably chosen from silicas and aluminas. The hydrophilic silicas used in the context of the invention consist of silicon oxide. These are pyrogenic silicas with no specific treatment, unlike hydrophobic silicas which are pyrogenic silicas having undergone a chemical treatment such as grafting with dimethylchlorosilane. It is not beyond the scope of the invention using silicas synthesized by another method of manufacture. Commonly used silicas are commercial products whose trade name is Aerosil® (Evonik supplier) or Cab-o-Sil® (Cabot supplier). These silicas are composed of primary particles nanometers (typically between 5 and 50 nm for pyrogenic silicas). These primary particles are associated to form aggregates. In use as a flow agent, silicas are found in different forms (elementary particles and aggregates). The powders or powder mixtures comprising hydrophilic flow agents used in the context of the invention may, where appropriate, be additive or contain different compounds. Among these compounds, mention may be made of reinforcing fillers, in particular mineral fillers such as carbon black, nanotubes, of carbon or non-carbon, fibers (glass, carbon, etc.), milled or not, stabilizing agents (light, particular UV, and heat), optical brighteners, dyes, pigments, energy-absorbing additives (including UV absorbers) or a combination of these fillers or additives. Examples: Flowability measurement: The flowability of these powders was carried out in glass funnels in the following manner: - Fill the glass funnels with a 17 or 12 mm orifice (FIG. 1) with the powder up to 5 mm from the edge. Close the bottom hole with your finger. With funnel 12 mm: of = 39.2 mm do = 12 mm h = 106 mm h1 = 83 mm and for funnel 17 mm: of = 42, 0 mm do = 17 mm h = 112 mm h1 = 67 mm - Measure to the chronometer the flow time of the powder. - If the flow is not done, tap the funnel with a spatula. Repeat the operation if necessary. - Note the flow time and the number of hits typed using the spatula. Estimation of Coalescence: The coalescence of the powders is estimated by the following protocol: powder deposition on a steel plate; baking, at 340 ° C. for 15 minutes, of the powder-coated plate; observation of the plate coated after cooling after leaving the oven - 13 - The coalescence will be judged all the better that the steel plate will become invisible following the coalescence / filming of the powder.
    [0005] EXAMPLE 1 A Kepstan® 6003 PL powder from Arkema, containing 60% terephthalic units with respect to the sum of the terephthalic and isophthalic units, whose particle size has a dv50 of 50 μm plus or minus 5 μm, was added with 0.4% CAB-O-Sil® TS-610 silica in a high speed Magimix robot for 100 seconds. The Dv50 is also called the volume median diameter which corresponds to the value of the particle size that divides the examined particle population into exactly two. The Dv50 is measured according to the ISO 9276 standard - parts 1 to 6. In the present description, a Malvern Mastersizer 2000 particle size analyzer is used, and the measurement is made in liquid way by laser diffraction on the powder.
    [0006] The CAB-0-SilED TS-610 silica is a fumed silica rendered hydrophobic by treatment with dimethyl chlorosilane. It will be noted later "TS-610".
    [0007] The powder has excellent flowability (time <10s, 0 counts for a funnel 17mm) but the coalescence, estimated as described above, is very low, the steel plate being still clearly visible. The silica can therefore be at a high level an anti-coalescing agent. EXAMPLE 2 A Kepstan® 6003 PL powder from Arkema, containing 60% of terephthalic units relative to the sum of the terephthalic and isophthalic units, whose particle size has a dv50 of 50 μm plus or minus 5 μm was CAB-O-Sil® TS-610 silica additive in a Magimix robot at high speed for 100 seconds.
    [0008] A second sample of the same Kepstan powder is additive of CAB-O-Sil® M-5 silica according to the same protocol. CAB-O-Sil® M-5 silica is a hydrophilic pyrogenic silica that has not been specifically treated. It will be noted later "M-5".
    [0009] The flowability results of the two additive powders are given in Table 1 compared to the powder without silica.
    [0010] Table 1 Without silica 0.1% TS 0.2% TS 0.1'V ° M5 0.2% M5 610 610 Flowability Time (s) 90 60 12 80 22 funnel 12 mm Number multi multi 3 multi 14 shots Flowability funnel 17 mm Time (s) 48 13 9 22 12 Number 40 3 0 10 1 shots The term multi is used when you tap on the funnel continuously.25 - It is found that both types of silica improve the flowability and are therefore 2 potential flow agents for PEKK.
    [0011] Example 3: Another Kepstan® 6003 PL powder from Arkema is additivated with Magimix or 0.05% silica CAB-O-Sil® TS-610 or 0.05% CAB-O-Sil® M-5.
    [0012] These powders are first stored at 23 ° C and 50% RH until saturation in moisture (case, for example, a storage of the powder before use in the machine). The moisture content is measured by the Karl Fischer method (desorption of water from Kepstan® powder by a 20 min treatment at 250 ° C). On the other hand, the powders are dried overnight at 140 ° C. The humidity level is also measured by the Karl Fischer method (same protocol as above). The flowability results of the two additive powders with different moisture contents are given in Table 2. Table 2 Moisture content 0.05% TS 610 0.05% 1 025 0 0 0 0 0 0 0 Flowability Time (s) 7 5 6 6 funnel 17 mm Number 0 0 0 0 strokes 25 Humidity levels of 0.5% and 0.53% correspond to the state of the material saturated with moisture at 23 ° C and 50% RH. The moisture content of 0.25% corresponds to the state of the material after drying at 140 ° C for 1 night. Moisture levels are unaffected by the nature of the silica.
    [0013] It appears that, regardless of the silica used, the flowability is not affected by the moisture content. In particular, no deterioration of the flowability is observed for moisture-saturated powders (23 ° C., 50% RH) even in the case of using a hydrophilic silica as a flow agent. EXAMPLE 4 Three samples of Example 2 (not additive, additive of 0.2% of hydrophobic silica (TS-610), additive of 0.2% of hydrophilic silica (M-5)) are deposited on three steel plates. These coated plates are placed in an oven maintained at 340 ° C. for 15 minutes.
    [0014] They are then cooled and then, visually and under binocular (Zeiss Stemi SV11), the PEKK coating is observed on the surface of the plates (FIGS. 2 and 3). Visually (Fig. 2), a much smoother surface is observed when the hydrophilic silica (M-5) is used demonstrating good coalescence of the powder during baking. Without silica and with TS-610 silica, the coating is not continuous and, therefore, the steel plate remains locally visible.
    [0015] The binocular images (FIG. 3) confirm the previous observations: there are areas where locally the steel plate is always seen in the case of the non-additive powder and the powder additized with 0.2% TS silica. -610, while, in the case of the silica-additive powder M-5, the steel plate is no longer visible. This confirms the best coalescence of the powder additive M-5 during the oven.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A composition comprising from 99.6 to 99.99% by weight of at least one powder of at least one polyarylene ether ketone and 0.01 to 0.4% by weight of a hydrophilic flow agent, said hydrophilic flow being characterized by a weight gain (amount of water absorbed) after 5 days of conditioning at a relative humidity of 95% greater than 0.5%, said weight gain of the flow agent being determined by Karl Fisher measurement after desorption of water by a treatment of 15 min at 170 ° C.
    [0002]
    The composition of claim 1 wherein the hydrophilic flow agent is a hydrophilic silica.
    [0003]
    3. Composition according to claim 1 wherein at least one poly-arylene-ether-ketone is PEKK.
    [0004]
    4. The composition of claim 3 wherein the PEKK has a weight percent terephthalic unit based on the sum of the terephthalic and isophthalic units of between 55% and 85%.
    [0005]
    5. The composition according to claim 3, in which in addition to PEKK, a powder of PEK, PEEKEK, PEEK, PEKEKK, PEKK of different chemical structure is added, the PEKK representing more than 50% by weight, including the limit.
    [0006]
    The composition of claim 1 containing a filler.
    [0007]
    7. Composition according to claim 1 containing at least one additive.
    [0008]
    8. Use of a composition according to one of claims 1 to 7 in a laser sintering process.
    [0009]
    9. Object obtained from a composition according to
    [0010]
    10. one of claims 1 to 7.
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    EP1674497A1|2004-12-21|2006-06-28|Degussa AG|Use of polyarylene ether ketone powder in a powder-based tridimensional tool-less method of manufacturing and shaped articles obtained therefrom|
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    JP4192073B2|2003-11-06|2008-12-03|電気化学工業株式会社|Method for producing silica powder|
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 7 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 8 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 9 |
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