WO2008087358A2 - Poudre de polyamide coeur-ecorce - Google Patents
Poudre de polyamide coeur-ecorce Download PDFInfo
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- WO2008087358A2 WO2008087358A2 PCT/FR2007/052621 FR2007052621W WO2008087358A2 WO 2008087358 A2 WO2008087358 A2 WO 2008087358A2 FR 2007052621 W FR2007052621 W FR 2007052621W WO 2008087358 A2 WO2008087358 A2 WO 2008087358A2
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- powder
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- temperature
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/02—Moulding by agglomerating
- B29C67/04—Sintering
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
Definitions
- the present invention relates to a process for preparing a new polyamide 12, polyamide 6 or polyamide 6/12 powder seeded with an organic filler, this powder having a lower crystallization temperature than the same powder inoculated with a mineral filler. .
- This is an anionic type synthesis from lactam.
- the powders obtained have a mean diameter of between 8 ⁇ m and 100 ⁇ m.
- These polyamide powders are, in particular, useful in the technology of agglomeration of polyamide powders by fusion caused by radiation such as for example a laser beam (laser sintering), infrared radiation or UV radiation (UV curing) in the field of cosmetic compositions or in composites.
- the technology of agglomeration of polyamide powders under a laser beam is used to manufacture objects in three dimensions such as prototypes and models.
- a thin layer of polyamide powder is deposited on a horizontal plate held in a chamber heated to a temperature between the crystallization temperature (Tc) and the melting temperature (Tf) of the polyamide powder.
- the laser agglomerates 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.
- 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.
- the powder has the largest possible difference Tf - Tc in order to avoid the phenomena of deformation (or "curling") during manufacture. Indeed, at time t 0, ie immediately after the action of the laser beam, the temperature of the sample is greater than the crystallization temperature (Tc) of the powder but the addition of a new layer of colder powder quickly drops the temperature of the room below the (Tc) and causes deformations.
- Tc crystallization temperature
- a new seeded polyamide powder has now been discovered whose powder particles consist of a bark of PA6, PA12 or PA6 / 12 and a core of PA6, PA11, PA12, PA6 / 12, PA6.12, PA6. .6, PA8, PA4.
- the use of this powder in an agglomeration technology defined above is particularly advantageous because the latter has a difference Tf-Tc in absolute value increased compared to the usual powders.
- the particle of powder can have a bark and a heart of the same nature PA but of different molecular masses M: bark and heart in PA6, bark and heart in PA12, bark and heart in PA6 / 12 or have a bark and a heart of nature PA different. In this case, we have for example:
- the present invention relates to a new powder, its use and its method of preparation by anionic polymerization of lauryllactam monomer, caprolactam or their mixture in solution in a solvent of said lactam or said mixture and in the presence of seeds which are particles of powder from PA6, PA1 1, PA12, PA6 / 12, PA6.12, PA6.6, PA8 and PA4, said polymerization being carried out in the presence:
- An activator a charge, said charge being powder particles of PA12, PA1 1,
- R1-NH-CO-R2 • an amide of formula R1-NH-CO-R2 wherein R1 may be replaced by an R3-CO-NH- or R3-O- and in which R1, R2 and R3 denote an aryl, alkyl or cycloalkyl the proportion of this compound being between 0.001 mol and 0.1 mol per 1000 g of monomers at a polymerization temperature> 70 ° C and ⁇ 150 ° C.
- the seeded powder obtained at the end of the polymerization is insoluble in the solvent of the lactam previously introduced into the reaction medium. Seeding is when the thickness of the polymer layer of the final seeded powder particle is greater than the radius of the feed and conversely, it is called coating when the thickness of the polymer layer of the final coated particle is less than the radius of the load.
- the subject of the invention is a particle of seeded polyamide (PA) powder consisting of a polyamide bark and a polyamide core, the core and the bark being of identical polyamide nature but of different molecular mass or of different polyamide nature. .
- the particle of seeded polyamide (PA) powder is characterized in that the bark is made of PA6, PA12 or PA6 / 12 and the core of PA6, PA1 1, PA12, PA6 / 12, PA6. 12, PA6.6, PA8 or PA4, the heart and the bark being of identical PA nature but of different molecular mass or different PA nature.
- the particle whose bark has a melting temperature Tf1 and a crystallization temperature Td and whose core has a melting temperature Tf2 and a crystallization temperature Tc2, characterized in that the difference in absolute value between TfI-Td and / or between Tf2-Tc2 is greater than the difference in absolute value between the melting temperature and the crystallization temperature of a particle of powder seeded by a mineral filler and whose bark is PA6, PA12 or PA6 / 12.
- the particle of powder is characterized in that it has a bark and a heart of the same nature PA, ie bark and heart PA6, bark and heart PA12 or bark and heart PA6 / 12.
- the particle is characterized in that it has a bark PA6 and a core selected from PA1 1, PA12, PA6 / 12, PA6.12, PA6.6, PA8 and A4 P.
- the particle is characterized in that it has a bark PA12 and a core selected from PA6, PA1 1, PA6 / 12, PA6.12, PA6.6, PA8 and A4 P. According to one embodiment, the particle is characterized in that it has a bark in PA6 / 12 and a core selected from PA6, PA1 1, PA12, PA6.12, PA6.6, PA8 and P A4.
- the subject of the invention is also a method for manufacturing anionic polymerization powder particle in solution in a solvent, characterized in that said polymerization of lactam 6, of lactam 12 or of their mixture is carried out in the presence of a catalyst, an activator, at least one amide selected from N, N'-alkylenebisamide and an organic filler.
- the process is characterized in that the organic filler is selected from PA6, PA1, PA12, PA6 / 12, PA6.12, PA6.6, PA8 and PA4.
- the process is characterized in that the N, N'-alkylenebisamide is chosen from EBS and EBO.
- the process is characterized in that, in addition to N, N'-alkylenebisamide, another amide chosen from oleamide, N-stearamide, isostearamide and erucamide .
- the invention also relates to the use of the powder in composites, substrate coatings, transfer papers or for manufacturing cosmetic compositions.
- the use of the powder for making objects by agglomeration of said powder by melting caused by a radiation selected from a laser beam, infrared radiation or UV radiation.
- the invention also relates to an object manufacturing method by agglomeration of the powder in which: a. A thin layer of powder (layer 1) is deposited on a horizontal plate held in a chamber heated to a temperature between the crystallization temperature (Tc) and the melting temperature (Tf) of said powder, b. a laser agglomerates powder particles at different points of the powder layer (layer 1) according to a geometry corresponding to the object to be manufactured, c. the horizontal plate is lowered by a value corresponding to the thickness of a layer of powder, then a new layer of powder is deposited (layer 2), d. the laser agglomerates the powder particles of the powder layer (layer 2) according to a geometry corresponding to this new slice of the object to be manufactured, e.
- the horizontal plate is lowered by a value corresponding to the thickness of a layer of powder, then a new layer of powder is deposited, f. the laser agglomerates the powder particles of the powder layer according to a geometry corresponding to this new slice of the object to be manufactured, g. the previous steps are repeated until the object is completed; h. it is slowly cooled below the crystallization temperature (Tc).
- Tc crystallization temperature
- the solvent used dissolves the monomer but not the polymer particles that form during the polymerization.
- the solvent are given in patent EP192515.
- the solvent is a paraffinic hydrocarbon fraction whose boiling range is between 120 and 170 ° C, preferably between 140 and 170 ° C.
- the solvent may be supersaturated to the monomer at the initiation temperature, i.e., at the temperature at which the polymerization begins.
- Various means make it possible to supersaturate the solvent to monomer.
- One of these means may consist of saturate the solvent in monomer at a temperature higher than that of initiation, then lower the temperature to the initiation temperature.
- Another way may be to substantially saturate the monomer solvent at the initiation temperature, then to add, always at this temperature, a primary amide containing preferably 12 to 22 carbon atoms, such as oleamide, N-stearamide, erucamide, isostearamide or N, N'-alkylenebisamide, examples of which are given below.
- reaction medium contains the monomer dissolved in the solvent at a concentration remote from the supersaturation at the initiation temperature.
- a catalyst selected from the usual catalysts of the anionic polymerization of lactams is used. This is a base strong enough to lead to a lactamate after reaction with the lactam.
- a combination of several catalysts is possible. By way of non-limiting examples, mention may be made of sodium hydride, potassium hydride, sodium, methylate and / or sodium ethoxide.
- the amount of catalyst (s) introduced can generally vary between 0.5 and 3 moles per 100 moles of monomer.
- the activator is also added whose role is to provoke and / or accelerate the polymerization.
- the activator is chosen from lactams-N-carboxyanilides, (mono) isocyanates, polyisocyanates, carbodiimides, cyanamides, acyllactams and acylcarbamates, triazines, ureas, N-substituted imides, esters and trichloride. of phosphorus. It may also be a mixture of several activators.
- the activator may also optionally be formed in situ, for example, by reacting an alkyl isocyanate with the lactam to give an acyl lactam.
- the catalyst / activator molar ratio is between 0.2 and 2, preferably between 0.8 and 1.2.
- At least one amide one of which is always an N, N'-alkylenebisamide, is also added as indicated in EP192515.
- the amount of N, N'-alkylenebisamide (s) introduced is generally of the order of 0.001 to 4 moles, preferably 0.075 to 2 moles per 100 moles of monomer.
- N, N'-alkylenebis amides particularly recommended mention may be made of N, N'-alkylene bis amides of fatty acids and better still:
- EBS and / or EBO are used.
- a primary amide preferably containing from 12 to 22 carbon atoms. It may be chosen from: oleamide, N-stearamide, isosteramide and erucamide.
- the organic filler it is homo or copolyamide polyamide powders, preferably of PA12, PA1 1, PA6, PA6 / 12, PA 6.12, PA 6.6, PA8, PA4 (for example powders of Orgasol® from Arkema, Vestosint® powders from
- the amount of organic filler and the diameter of said fillers make it possible to orient in the desired direction (small particles or large particles) the size of the final particles obtained at the end of the polymerization. • Other charges or additives
- Antioxidants for anti-UV, plasticizers, (7) provided that all these compounds are dry and inert vis-à-vis the reaction medium.
- the anionic polymerization is conducted continuously or preferably batchwise.
- the solvent is introduced, then simultaneously or successively the monomer (s), optionally an N, N'-alkylenebisamide, the filler, the catalyst and the activator. It is recommended to first introduce the solvent and the monomer (s) and then remove all traces of water, for example using azeotropic distillation, then add the catalyst once the anhydrous medium.
- the charge can be introduced for example after the introduction of the monomer (s). It may be advantageous to avoid caking or loss of control of the polymerization to introduce the activator not all at once but in increments or at a given feed rate.
- the reaction is carried out at atmospheric pressure or under a slightly higher pressure (partial pressure of the hot solvent) and at a temperature of between 20 ° C. and the boiling point of the solvent.
- the initiation and polymerization temperature of the lactams is in general between 70 and 150 ° C, preferably between 80 and 130 ° C and advantageously ⁇ 120 ° C and> 90 ° C.
- the weight ratio [organic load / monomer (s) introduced into the reaction medium] expressed in% is between 0.001 and 65%, preferably between 0.005 and 45%, even more preferentially between 0.01 and 65%. and 30%, and advantageously between 0.05 and 20%.
- the powders according to the invention can be used in the context of the method of manufacturing objects by melting caused by a laser beam (laser sintering), IR radiation or UV radiation.
- laser sintering laser sintering
- IR radiation IR radiation
- UV radiation UV radiation.
- the laser sintering technique is described in patent application EP1571173 of the applicant.
- the particle size distribution of the powders according to the invention is determined according to the usual techniques using a Coulter LS230 granulometer of the company.
- Beckman-Coulter From the particle size distribution, it is possible to determine the average volume diameter with the log version of the logarithmic version.
- the analysis of the powders is made according to the standard ISO 11357-3 "Plastics - differential scanning calorimetry (DSC) Part 3: Determination of temperature and enthalpy of melting and crystallization.”
- DSC differential scanning calorimetry
- AEROSIL® R972 silicon finely divided. After stirring at 300 rpm, the mixture is gradually heated to 110 ° C., and then 290 ml of solvent are distilled off under vacuum in order to azeotropically remove any trace of water that may be present.
- the anionic catalyst 7.2 g of sodium hydride at 60% purity in oil, are rapidly introduced under nitrogen and the stirring is increased to 720 rpm under nitrogen at room temperature. 1 10 ° C for 30 minutes.
- the temperature is brought to 96 ° C. and, thanks to a small dosing pump, a continuous injection into the reaction medium of the chosen activator, namely stearyl isocyanate (32.9 g filled to 314 g with solvent) according to the following schedule:
- the particle size is between 1 and 40 ⁇ m with an average particle diameter of 9.9 ⁇ m, a difference between type of 1, 54 and an SSA of 16.8 m 2 / g without agglomerates.
- the first melting point is 163 ° C. and the solution viscosity 0.84 dl / g.
- EXAMPLE 2 (PA6 / 12 Seeded PA12) 2800 ml of solvent are introduced into the reactor maintained under nitrogen, followed successively by 108 g of caprolactam, 679 g of dry lauryl lactam, 14.4 g of EBS and 12 g of ORGASOL. ® 2001 UD NAT1 (PA12 powder 5 ⁇ m in diameter) finely divided. After stirring at 300 rpm, the mixture is gradually heated to 110 ° C. and then 290 ml of solvent are distilled off under vacuum to azeotropically remove any water that may be present.
- the anionic catalyst 7.2 g of sodium hydride at 60% purity in oil, are rapidly introduced under nitrogen and the stirring is increased to 720 rpm under nitrogen at 1 ° C. 10 ° C for 30 minutes.
- the temperature is brought to 96 ° C. and, thanks to a small dosing pump, a continuous injection into the reaction medium of the chosen activator, namely stearyl isocyanate (32.9 g filled to 314 g with solvent) according to the following schedule:
- the reactor is almost clean.
- the particle size is between 3 and 35 ⁇ m with an average particle diameter of 11.8 ⁇ m, a standard deviation of 1.27 and an SSA of 9.3 m 2 / g. without agglomerates.
- the bark and core melting temperatures are respectively 161.5 ° C and 173.7 ° C.
- Comparative Example 3 (PA6 / 12 + silica) 2800 ml of solvent are introduced into the reactor maintained under nitrogen, followed successively by 108 g of caprolactam, 791 g of dry lauryl lactam, 24.7 g of EBS and 16.2 g of AEROSIL® R972 (silica) finely divided. After stirring at 300 rpm, the mixture is gradually heated to 110 ° C. and then 290 ml of solvent are distilled off under vacuum in order to azeotropically remove any trace of water that may be present. After returning to atmospheric pressure, the anionic catalyst, 7.2 g of sodium hydride at 60% purity in oil, are rapidly introduced under nitrogen and the stirring is increased to 720 rpm under nitrogen at room temperature. 1 10 ° C for 30 minutes.
- the temperature is brought to 105 ° C. and, thanks to a small dosing pump, a continuous injection into the reaction medium of the chosen activator, namely stearyl isocyanate (32.9 g filled to 324 g with solvent) according to the following schedule:
- the temperature is maintained at 105 ° C. for 360 minutes of injection and is then raised to 110 ° C. over 60 minutes and maintained at 110 ° C. for a further 3 hours after the end of introduction of the isocyanate.
- the reactor is almost clean.
- the particle size is between 2 and 70 ⁇ m with an average particle diameter of 23.8 ⁇ m, a standard deviation of 1.65 without agglomerates.
- the anionic catalyst 5.4 g of sodium hydride at 60% purity in oil, is rapidly introduced under nitrogen and the stirring is increased to 720 rpm under nitrogen at room temperature. 1 10 ° C for 30 minutes. Then, the temperature is brought to 96 ° C. and, thanks to a small dosing pump, a continuous injection is made into the reaction medium of the chosen activator, namely stearyl isocyanate (16.45 g filled to 324 g with solvent) according to the following schedule:
- the temperature is maintained at 96 ° C for 360 minutes during the injection, then rose to 110 ° C in 60 minutes and maintained at 110 ° C for another 3 hours after the end of introduction of the isocyanate .
- Example 5 PA6 Inoculated PA12 2800 ml of solvent are introduced into the reactor maintained under nitrogen, followed successively by 899 g of caprolactam, 7.2 g of EBS and 54 g of ORGASOL® 2001 EXD NAT1. After stirring at 300 rpm, the mixture is gradually heated to 110 ° C. and then 290 ml of solvent are distilled off under vacuum in order to azeotropically remove any trace of water that may be present. After returning to atmospheric pressure, the anionic catalyst, 5.8 g of sodium hydride at 60% purity in oil, is rapidly introduced under nitrogen and the stirring is increased at 550 rpm, under nitrogen. at 110 ° C for 30 minutes.
- NAT1 (PA6 powder). After stirring at 300 rpm, the mixture is gradually heated to 110 ° C., and then 290 ml of solvent are distilled off under vacuum in order to azeotropically remove any trace of water that may be present.
- the anionic catalyst 5.8 g of sodium hydride at 60% purity in oil, is rapidly introduced under nitrogen and the stirring is increased at 550 rpm, under nitrogen. at 110 ° C for 30 minutes.
- the temperature is brought back to 120 ° C. and it remains at this temperature for 60 minutes. Thanks to a small dosing pump, an injection is made continuous in the reaction medium of the chosen activator, namely stearyl isocyanate (37.3 g filled to 66.3 g with solvent) according to the following program:
- the temperature is maintained at 120 ° C for the first 215 minutes.
- the anionic catalyst 5.8 g of sodium hydride at 60% purity in oil
- the stirring is increased at 550 rpm, under nitrogen. at 110 ° C for 30 minutes.
- the temperature is brought back to 120 ° C. and it remains at this temperature for 60 minutes.
- a continuous injection into the reaction medium of the chosen activator namely stearyl isocyanate (37.3 g filled to 66.3 g with solvent) is carried out according to the following program:
- the anionic catalyst 2.7 g of sodium hydride at 60% purity in oil, are rapidly introduced under nitrogen and the stirring is increased at 550 rpm, under nitrogen. at 105 ° C for 30 minutes.
- the temperature is maintained at 105 ° C. for 360 minutes during the injection, then is raised to 110 ° C. in 30 minutes and maintained at 110 ° C. for 30 minutes, then is raised to 130 minutes in 30 minutes and maintained at 130 minutes. for another 3 hours after the end of introduction of the isocyanate.
- the anionic catalyst 2.7 g of sodium hydride at 60% purity in oil, are rapidly introduced under nitrogen and the stirring is increased at 550 rpm, under nitrogen. at 105 ° C for 30 minutes.
- a continuous injection into the reaction medium of the chosen activator namely stearyl isocyanate (19.2 g filled to 220.5 g with solvent) is carried out according to the following program:
- the anionic catalyst 2.7 g of sodium hydride at 60% purity in oil, are rapidly introduced under nitrogen and the stirring is increased at 550 rpm, under nitrogen. at 105 ° C for 30 minutes.
- the anionic catalyst 9 g of sodium hydride at 60% purity in oil
- the stirring is increased at 550 rpm under nitrogen at 1 ° C. 10 ° C for 30 minutes.
- the temperature is brought back to 81 ° C. and it remains at this temperature for 30 minutes.
- a continuous injection into the reaction medium of the chosen activator namely stearyl isocyanate (32.4 g filled to 323.9 g with solvent) is carried out according to the following program:
- the anionic catalyst 9 g of sodium hydride at 60% purity in oil, is rapidly introduced under nitrogen and the stirring is increased at 550 rpm under nitrogen at 1 ° C. 10 ° C for 30 minutes.
- the temperature is brought back to 81 ° C. and it remains at this temperature for 30 minutes.
- a continuous injection into the reaction medium of the chosen activator namely stearyl isocyanate (32.4 g filled to 323.9 g with solvent) is carried out according to the following program: > 53.9 g / h of isocyanate solution for 360 minutes.
- the temperature is maintained at 81 ° C during injection, then rose to 110 ° C in 60 minutes and maintained at 110 ° C for another 3 hours after the end of introduction of the isocyanate.
- the particle size is between 5 and 80 microns, the average particle diameter is 31 microns.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyamides (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07872030.7A EP2125933B1 (fr) | 2006-12-28 | 2007-12-26 | Poudre de polyamide coeur-ecorce |
US12/521,089 US9617384B2 (en) | 2006-12-28 | 2007-12-26 | Core-shell polyamide powder |
KR1020097013255A KR20090103893A (ko) | 2006-12-28 | 2007-12-26 | 코어-쉘 폴리아미드 분말 |
JP2009543510A JP5378232B2 (ja) | 2006-12-28 | 2007-12-26 | コア−シェルポリアミドの粉末 |
MX2009007022A MX2009007022A (es) | 2006-12-28 | 2007-12-26 | Polvo de poliamida de nucleo-corteza. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0656029A FR2910907B1 (fr) | 2006-12-28 | 2006-12-28 | Poudre de polyamide coeur-ecorce |
FR0656029 | 2006-12-28 |
Publications (2)
Publication Number | Publication Date |
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WO2008087358A2 true WO2008087358A2 (fr) | 2008-07-24 |
WO2008087358A3 WO2008087358A3 (fr) | 2008-09-25 |
Family
ID=38190851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2007/052621 WO2008087358A2 (fr) | 2006-12-28 | 2007-12-26 | Poudre de polyamide coeur-ecorce |
Country Status (9)
Country | Link |
---|---|
US (1) | US9617384B2 (fr) |
EP (1) | EP2125933B1 (fr) |
JP (1) | JP5378232B2 (fr) |
KR (1) | KR20090103893A (fr) |
CN (2) | CN101573395A (fr) |
FR (1) | FR2910907B1 (fr) |
MX (1) | MX2009007022A (fr) |
RU (1) | RU2009128972A (fr) |
WO (1) | WO2008087358A2 (fr) |
Cited By (1)
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US11577458B2 (en) | 2018-06-29 | 2023-02-14 | 3M Innovative Properties Company | Additive layer manufacturing method and articles |
Families Citing this family (10)
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FR2930555B1 (fr) | 2008-04-29 | 2012-08-24 | Arkema France | Procede pour augmenter l'ecart entre la temperature de fusion et la temperature de cristallisation d'une poudre de polyamide |
ES2617184T3 (es) * | 2012-02-15 | 2017-06-15 | Toray Industries, Inc. | Partículas de material compuesto de poliamida y método para producir las mismas |
FR3005660B1 (fr) * | 2013-05-17 | 2015-04-24 | Arkema France | Procede de reticulation en surface de particules de polymere |
US10544311B2 (en) | 2014-01-16 | 2020-01-28 | Hewlett-Packard Development Company, L.P. | Polymeric powder composition for three-dimensional (3D) printing |
PT107679A (pt) * | 2014-06-03 | 2015-12-03 | Univ Do Minho | Microcápsulas de poliamida e método para a sua produção |
FR3024658B1 (fr) * | 2014-08-05 | 2016-09-02 | Oreal | Procede de fabrication additive d'un objet tridimensionnel comprenant ou constituant une composition cosmetique par projection directe, et appareil associe |
US9617394B2 (en) * | 2015-04-15 | 2017-04-11 | Aeonclad Coatings, Llc | Coated particles for forming of continuous polymeric or metallic layers |
JP6866602B2 (ja) * | 2016-10-03 | 2021-04-28 | コニカミノルタ株式会社 | 粉末材料、立体造形物の製造方法 |
KR102262539B1 (ko) * | 2017-11-14 | 2021-06-08 | 한화솔루션 주식회사 | 활성화제 투입 방식 조절을 통한 폴리아마이드 제조방법 및 이에 의해 제조된 폴리아마이드 |
FR3095205B1 (fr) * | 2019-04-19 | 2021-09-10 | Arkema France | Particules de poudres de polyamide et leur utilisation dans les procedes d’agglomeration de poudre |
Citations (3)
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EP0192515A1 (fr) * | 1985-01-30 | 1986-08-27 | Elf Atochem S.A. | Procédé de fabrication de poudre de polyamide |
EP1413595A1 (fr) * | 2002-10-23 | 2004-04-28 | Atofina | Augmentation du point de fusion et de l'enthalpie de fusion des polyamides par un traitement à l'eau |
EP1571173A1 (fr) * | 2004-03-02 | 2005-09-07 | Arkema | Procédé de fabrication de poudre de polyamide-12 à point de fusion élevé |
Family Cites Families (6)
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DE2906647C2 (de) * | 1979-02-21 | 1980-12-11 | Chemische Werke Huels Ag, 4370 Marl | Verfahren zur Herstellung von pulver· förmigen Beschichtungsmittel!! auf der Basis von Polyamiden mit mindestens 10 aliphatisch gebundenen Kohlenstoffatomen pro Carbonamidgruppe |
FR2619385B1 (fr) * | 1987-08-11 | 1992-01-17 | Atochem | Poudre de polyamide constituee de particules a structure " rose des sables ". procede d'obtention de la poudre de polyamide |
DE19747309B4 (de) * | 1997-10-27 | 2007-11-15 | Degussa Gmbh | Verwendung eines Polyamids 12 für selektives Laser-Sintern |
US7468405B2 (en) * | 2002-10-23 | 2008-12-23 | Atofina | Increase in the melting point and the enthalpy of melting of polyamides by a water treatment |
US8124686B2 (en) * | 2004-03-02 | 2012-02-28 | Arkema France | Process for the manufacture of polyamide-12 powder with a high melting point |
JP2005307096A (ja) * | 2004-04-26 | 2005-11-04 | Shinto Fine Co Ltd | ポリアミド粒子及びその製造方法 |
-
2006
- 2006-12-28 FR FR0656029A patent/FR2910907B1/fr not_active Expired - Fee Related
-
2007
- 2007-12-26 EP EP07872030.7A patent/EP2125933B1/fr active Active
- 2007-12-26 US US12/521,089 patent/US9617384B2/en active Active
- 2007-12-26 CN CNA2007800486516A patent/CN101573395A/zh active Pending
- 2007-12-26 RU RU2009128972/04A patent/RU2009128972A/ru not_active Application Discontinuation
- 2007-12-26 JP JP2009543510A patent/JP5378232B2/ja active Active
- 2007-12-26 MX MX2009007022A patent/MX2009007022A/es active IP Right Grant
- 2007-12-26 KR KR1020097013255A patent/KR20090103893A/ko active Search and Examination
- 2007-12-26 WO PCT/FR2007/052621 patent/WO2008087358A2/fr active Application Filing
- 2007-12-26 CN CN201410800943.2A patent/CN104558592A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0192515A1 (fr) * | 1985-01-30 | 1986-08-27 | Elf Atochem S.A. | Procédé de fabrication de poudre de polyamide |
EP1413595A1 (fr) * | 2002-10-23 | 2004-04-28 | Atofina | Augmentation du point de fusion et de l'enthalpie de fusion des polyamides par un traitement à l'eau |
EP1571173A1 (fr) * | 2004-03-02 | 2005-09-07 | Arkema | Procédé de fabrication de poudre de polyamide-12 à point de fusion élevé |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US11577458B2 (en) | 2018-06-29 | 2023-02-14 | 3M Innovative Properties Company | Additive layer manufacturing method and articles |
Also Published As
Publication number | Publication date |
---|---|
US9617384B2 (en) | 2017-04-11 |
MX2009007022A (es) | 2009-07-10 |
EP2125933B1 (fr) | 2018-07-18 |
JP2010514877A (ja) | 2010-05-06 |
EP2125933A2 (fr) | 2009-12-02 |
CN104558592A (zh) | 2015-04-29 |
FR2910907A1 (fr) | 2008-07-04 |
US20100098880A1 (en) | 2010-04-22 |
JP5378232B2 (ja) | 2013-12-25 |
KR20090103893A (ko) | 2009-10-01 |
WO2008087358A3 (fr) | 2008-09-25 |
RU2009128972A (ru) | 2011-02-10 |
FR2910907B1 (fr) | 2009-02-20 |
CN101573395A (zh) | 2009-11-04 |
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