WO2007115977A1 - Procede de preparation de particules a base de polymere thermoplastique et poudre ainsi obtenue - Google Patents
Procede de preparation de particules a base de polymere thermoplastique et poudre ainsi obtenue Download PDFInfo
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- WO2007115977A1 WO2007115977A1 PCT/EP2007/053251 EP2007053251W WO2007115977A1 WO 2007115977 A1 WO2007115977 A1 WO 2007115977A1 EP 2007053251 W EP2007053251 W EP 2007053251W WO 2007115977 A1 WO2007115977 A1 WO 2007115977A1
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- polymer
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- additive
- thermoplastic material
- mixture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/793—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling upstream of the plasticising zone, e.g. heating in the hopper
- B29C48/797—Cooling
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
- B29C48/83—Heating or cooling the cylinders
- B29C48/832—Heating
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
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- 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
- C08G69/46—Post-polymerisation treatment
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- 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
- 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
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B2009/125—Micropellets, microgranules, microparticles
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- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the invention relates to a powder preparation process consisting of particles based on thermoplastic polymer.
- the process of the invention more particularly comprises steps of preparing a mixture comprising the thermoplastic polymer and two additives in the molten state, cooling the mixture and recovering the powder by disintegration. It also relates to the powder obtainable by the process of the invention.
- thermoplastic polymer powders such as polyamide powders
- Thermoplastic polymer powders are used in particular as an additive in paints, for example in paints for coating sports floors to have anti-slip properties.
- Thermoplastic polymer powders are also introduced into cosmetic products such as sunscreens, for body or facial care and make-up removers. They are also used in the field of inks and papers.
- thermoplastic polymer powders Various processes for obtaining thermoplastic polymer powders are known to those skilled in the art.
- Thermoplastic polymer powders may be obtained for example by grinding or cryomilling thermoplastic polymer granules of average initial diameter of the order of 3 mm.
- these mechanical transformations by size reduction often result in particles of irregular shape and size rarely less than 100 microns.
- the size distribution of these particles is often wide and these can hardly be implemented on an industrial scale.
- thermoplastic polymer powders by dissolving polymer in a solvent and then precipitating.
- polymer powders such as polyamide by anionic polymerization of lactams in solution.
- the polymerization is carried out in the presence of the monomers, a solvent of the monomers, an initiator, a catalyst, an activator and the polymerization is carried out with stirring at a temperature of 1 l O'O.
- This process is specific to polyamides obtained from monomers of lactam type. It is not very flexible and does not make it possible to diversify the nature of the powders as a function of the final properties of the desired powder, by varying the nature of the monomers for example. It is also known to obtain copolyesteramide powders by anionic polymerization of lactams and lactones.
- the required particle size of the powder varies. For example, in the field of paint and varnishes, the required particle size varies from 0.1 to 10 ⁇ m; in the field of cosmetics the powders have a particle size of between 5 and 10 ⁇ m; in the field of rotomoulding, the particle size varies from 300 to 500 ⁇ m.
- powders having a determined and targeted particle size are sought, as well as flexible processes for the preparation of powder making it possible to diversify the particle size of the powder.
- One of the aims of the invention is to propose a process for manufacturing a thermoplastic material powder comprising particles of determined size, which may be of small size, and of substantially regular shape, having the advantages mentioned above.
- the invention proposes a process for manufacturing a powder of thermoplastic material comprising particles with a determined average diameter of less than 1 mm, comprising the following steps: a. Forming a molten mixture of said thermoplastic material P with at least one additive A to obtain a dispersion of discrete particles of the thermoplastic material P, said additive A being formed by a polymeric material comprising at least a part of its structure compatible with said thermoplastic material P and at least part of its incompatible and insoluble structure in said thermoplastic material P b. Cooling said mixture to a temperature below the softening temperature of the thermoplastic material P, vs. Process said cooled mixture to cause disintegration of the discrete particles of thermoplastic material P at least one insoluble compound and not compatible with the thermoplastic material P being introduced in step a), to obtain particles of desired average diameter
- the formation of the mixture is obtained by melting thermoplastic material and adding additive A and compound B in solid or molten form and applying a mixing energy to obtain the formation of particles. discrete thermoplastic material dispersed in an advantageously continuous phase formed by the additive A and the compound B.
- This mixture can be obtained in another embodiment of the invention, by solid state mixing of particles of said thermoplastic material P and particles of said additive A and particles of said compound B, and melting of the mixture of particles with application. on the melted mixture of a mixing energy to obtain the formation of discrete particles of thermoplastic material P dispersed in an advantageously continuous phase formed by the compound A and the compound B.
- Additive A and compound B may be added simultaneously or successively. When additive A and compound B are added successively, additive A is preferably added before compound B.
- the mass ratios R1 and R2 are defined as follows:
- R 1 is the mass ratio (mass of additive A + mass of compound B) / (mass of additive A + mass of compound B + mass of material P)
- R 2 is the mass ratio (mass of compound B) / (mass of additive A + mass of compound B).
- P / additive A / compound B there is generally a linear relationship, for a selected particle size, between Ri and R 2 . This linear relationship may vary depending on the mixing conditions of the P / additive A / compound B.
- the judicious choice of the ratio Ri and the ratio R 2 as defined above in the process of the invention makes it possible in particular to obtain powders of particles of determined average diameter.
- the method of the invention makes it possible to control the particle size of the powder. It makes it possible to obtain powders whose particle size is chosen and targeted.
- the process is flexible, the size of the particles of the powder can be chosen in a wide range of between 0.1 and 800 microns.
- the additive A, the compound B and the thermoplastic material P are introduced in step a) in a mass ratio R 1 (additive A + compound B) / (additive A + compound B + material P) of between 0.01 and 0.6. preferably between 0.01 and 0.5.
- the concentration by weight of additive A in the mixture advantageously between 1% and 50%, preferably between 3 and 30%.
- the weight concentration of additive B in the mixture is advantageously between 1% and 50%, preferably between 3 and 30%.
- the mixture can be obtained by any suitable device such as screw mixers or agitators compatible with the temperature and pressure conditions used for the implementation of thermoplastic materials.
- the molten mixture is shaped before the cooling step, for example in the form of filaments or rods.
- This shaping can be advantageously carried out by an extrusion process through a die.
- this molten mixture is preferably produced in an extruder feeding the extrusion die.
- Cooling of the molten mixture can be achieved by any suitable means. Of these, air cooling or dipping in a liquid is preferred.
- the step of recovering the thermoplastic material powder advantageously consists in a disintegration treatment of the discrete particles of thermoplastic material.
- This disintegration can be obtained by applying a shearing force on the cooled mixture.
- disintegration is meant the action of separating the discrete particles of thermoplastic material from the other elements of the mixture.
- the disintegration of the particles of thermoplastic material is obtained by dipping the cooled melt in a liquid, non-solvent of the thermoplastic material and advantageously solvent of the additive A and compound B.
- the process of the invention makes it possible to manufacture powders from any thermoplastic material.
- thermoplastic polymer By way of example of a thermoplastic polymer, mention may be made of polyamides, polyesters, polyurethanes, polyolefins such as polyethylene or polypropylene, polystyrene, and the like.
- the preferred thermoplastic polymers are polyamides. Any polyamide known to those skilled in the art can be used in the context of the invention.
- the polyamide is generally a polyamide of the type obtained by polycondensation from dicarboxylic acids and diamines, or of the type obtained by polycondensation of lactams and / or amino acids.
- the polyamide of the invention may be a mixture of polyamides of different types and / or of the same type, and / or copolymers obtained from different monomers corresponding to the same type and / or to different types of polyamide.
- polyamide 6 By way of example of a polyamide which may be suitable for the invention, mention may be made of polyamide 6, polyamide 6,6, polyamide 11, polyamide 12 and polyamides 4,6; 6.10; 6.12; 12.12, 6.36; semi-aromatic polyamides, for example polyphthalamides obtained from terephthalic and / or isophthalic acid, such as the polyamide sold under the trade name AMODEL, their copolymers and alloys.
- the polyamide is chosen from polyamide 6, polyamide 6,6, their mixtures and copolymers.
- the thermoplastic polymer is a polymer comprising star macromolecular chains.
- Polymers comprising such star macromolecular chains are for example described in documents FR 2,743,077, FR 2,779,730, US 5,959,069, EP 0.632.703, EP 0.682.057 and EP 0.832.149. These compounds are known to have improved fluidity compared to linear polyamides of the same molecular weight.
- thermoplastic polymer is a polycondensate consisting of:
- -XY- is a radical resulting from the polycondensation of two reactive functions F 1 and F 2 such that
- - F 1 is the precursor of the radical -X- and F 2 the precursor of the radical -Y- or vice versa, - the functions F 1 can not react between them by condensation
- condensation A is a covalent bond or an aliphatic hydrocarbon radical which may comprise heteroatoms and comprising from 1 to 20 carbon atoms.
- R2 is a branched or unbranched aliphatic or aromatic hydrocarbon radical containing from 2 to 20 carbon atoms.
- R3, R4 represents hydrogen, a hydroxyl radical or a hydrocarbon radical
- - Ri is a hydrocarbon radical comprising at least 2 carbon atoms, linear or cyclic, aromatic or aliphatic and may include heteroatoms.
- n, m and p each represent a number between 50 and 500, preferably between 100 and 400.
- polycondensate is described in the application WO 05/019510 incorporated by reference.
- polycondensate is a polyamide consisting of:
- Y is the radical - C - when X represents the radical - N -,
- A is a covalent bond or an aliphatic hydrocarbon radical which may comprise heteroatoms and comprising from 1 to 20 carbon atoms.
- R2 is a branched or unbranched aliphatic or aromatic hydrocarbon radical containing from 2 to 20 carbon atoms.
- R3 represents hydrogen, a hydroxyl radical or a hydrocarbon radical
- R5 represents hydrogen or a hydrocarbon radical comprising from 1 to 6 carbon atoms
- - R- is a hydrocarbon radical comprising at least 2 carbon atoms, linear or cyclic, aromatic or aliphatic and may comprise heteroatoms.
- n, m and p each represent a number between 50 and 500, preferably between 100 and 400.
- the thermoplastic polymers used in the invention may contain various additives such as mattifying agents, heat stabilizers, light stabilizers, pigments, dyes, fillers, in particular abrasive fillers.
- abrasive fillers such as mattifying agents, heat stabilizers, light stabilizers, pigments, dyes, fillers, in particular abrasive fillers.
- abrasive fillers such as mattifying agents, heat stabilizers, light stabilizers, pigments, dyes, fillers, in particular abrasive fillers.
- titanium oxide, zinc oxide, cerium oxide, silica or zinc sulphide used as matting and / or abrasive.
- the method of the invention can implement one or more additives A.
- the additive A is advantageously a block, sequence, comb, hyperbranched or star-type polymer.
- the structure compatible with the thermoplastic material forms a block, a sequence, the skeleton or the teeth of the comb, the heart or branches of the polymer star or hyperbranché.
- the compatible structure of the additive A comprises functions that are chemically identical to those of the thermoplastic polymer P.
- the additive A is chosen from the group consisting of a polymer D defined below or a hyperbranched polymer E comprising at least one block of polyalkylene oxide.
- Said polymer D is a polymer with thermoplastic properties comprising a block of thermoplastic polymer and at least one block of polyalkylene oxide such that: the block of thermoplastic polymer comprises a star or H macromolecular chain comprising at least one multifunctional core and at least one a branch or segment of thermoplastic polymer connected to the core, the core comprising at least three identical reactive functions
- the polyalkylene oxide block or blocks are connected to at least a portion of the free ends of the star or H macromolecular chain chosen from the ends of the thermoplastic polymer branch or segment and the ends of the multifunctional core;
- the star macromolecular chain of the polymer D is advantageously a star polyamide obtained by copolymerization from a monomer mixture comprising: a) a multifunctional compound comprising at least three identical reactive functional groups chosen from the amino function and the carboxylic acid function b) monomers of the following general formulas (IIa) and / or (Nb):
- R 1 , R 2 represent aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, substituted or unsubstituted, identical or different, comprising from 2 to 20 carbon atoms, and which may comprise heteroatoms,
- Y is a primary amine function when X represents a carboxylic acid function
- Y is a carboxylic acid function when X represents a primary amine function
- the macromolecular chain H of the thermoplastic polymer block of the polymer D is advantageously a polyamide H obtained by copolymerization from a monomer mixture comprising: a) a multifunctional compound comprising at least three identical reactive functions chosen from the amino function and the function carboxylic acid b) lactams and / or amino acids c) a difunctional compound selected from dicarboxylic acids or diamines, d) a monofunctional compound whose function is either an amino function or a carboxylic acid function, the functions of c) and d) being aminated when the functions of a) are acidic, the functions of c) and d) being acidic when the functions of a) are amino, the ratio of equivalents between the functional groups of a) and the sum of the functional groups of (c) and (d) being between 1, 5 and 0,66, the ratio in equivalents between the functional groups of c) and the groups ions of d) being between 0.17 and 1.5.
- the multifunctional compound of the star or H macromolecular chains is represented by formula (IV) in which :
- Ri is a hydrocarbon radical comprising at least two linear or cyclic, aromatic or aliphatic carbon atoms and which may comprise heteroatoms;
- A is a covalent bond or an aliphatic hydrocarbon radical comprising
- Z represents a primary amine radical or a carboxylic acid radical
- m is an integer between 3 and 8.
- the multifunctional compound is chosen from 2,2,6,6-tetra- ( ⁇ -carboxyethyl) -cyclohexanone, trimesic acid, 2,4,6-tri- (aminocaproic acid) -1,3, 5-triazine, 4-aminoethyl-1,8-octanediamine.
- the POA alkylene oxide block of the polymer D is preferably linear. It may be chosen from polyethylene oxide, polytrimethylene oxide and polytetramethylene oxide blocks. In the case where the block is based on polyethylene oxide, it may comprise at the ends of the block propylene glycol units.
- the polyalkylene oxide block of the polymer D is preferably a block of polyethylene oxide.
- hyperbranched polymer E a branched polymeric structure obtained by polymerization in the presence of compounds having a functionality greater than 2, and whose structure is not perfectly controlled. These are often statistical copolymers.
- the hyperbranched polymers can for example be obtained by reaction between, in particular, multifunctional monomers, for example trifunctional and bifunctional monomers, each of the monomers carrying at least two different reactive functions of polymerization.
- the hyperbranched polymer E of the invention is chosen from polyesters, polyesteramides and hyperbranched polyamides.
- the hyperbranched polymer E of the invention is preferably a hyperbranched copolyamide of the type obtained by reaction between: at least one monomer of formula (I) below:
- ARB f wherein A is a reactive polymerization function of a first type, B is a reactive polymerization function of a second type and capable of reacting with A, R is a hydrocarbon species, and f is the total number of reactive functions B per monomer: f> 2, preferably 2 ⁇ f ⁇ 10;
- R 1 is a substituted or unsubstituted hydrocarbon radical of the silicone, linear or branched alkyl, aromatic, alkylaryl, arylalkyl or cycloaliphatic type which may comprise unsaturations and / or heteroatoms;
- B is a reactive function of the same nature as B or B '; n> 1, preferably 1 ⁇ n ⁇ 100
- R 2 is a substituted or unsubstituted hydrocarbon radical, of the silicone type, linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic may include one or more unsaturations and / or one or more heteroatoms.
- A is a reactive function of the same nature as A or A ', the molar ratio 1/11 being defined as follows:
- copolyamides are described in WO 00/68298 A1, in particular on page 11, lines 3 to 6.
- the reactive polymerization functions A, B, A ', B' are advantageously chosen from the group comprising the carboxylic and amine functional groups.
- R 1 and / or R 2 are preferably polyoxyalkylenic amine radicals of Jeffamine® type.
- Compound B of the process of the invention is insoluble and not compatible with the thermoplastic material P.
- compound B has a chemical structure compatible with at least a part of the structure of additive A, in particular the structural part of A not compatible with the compound P.
- the compound B is a homopolymer of the non-compatible part of the additive A.
- Suitable for the invention are compounds belonging to the families of polysaccharides, polyoxyalkylene glycols, polyolefins, silicones, waxes, and the like.
- Compound B may be added separately from additive A or as a mixture with at least a portion of additive A.
- the process of the invention may use one or more compounds B.
- thermoplastic polymer granules P of additive A and of compound B or a mixture of thermoplastic polymer granules P, granules of additive A and granules of compound B can be carried out.
- the thermoplastic polymer P may also be in the form of granules, which is coated with additive A and / or compound B.
- Additive A and compound B may be introduced into polymer P during the polymerization process, advantageously at the end of the polymerization. It is also possible to introduce additive A and compound B into the polymer in the molten state.
- Step a) consists in preparing the mixture in the molten state, with stirring.
- Step a) is preferably carried out in an extruder, even more preferably in a twin-screw or multi-screw extruder.
- the mixture may be prepared according to a mode described above, and then introduced into the extrusion device implemented in step a).
- the mixture can be introduced in solid or liquid form, for example in the molten state.
- the mixture can also be prepared in situ in the same extrusion device as that implemented in step a).
- the stirring during step a) allows shearing of the composition and efficient mixing of the thermoplastic material, additive A and compound B.
- the shear energy applied is determined according to the nature of the products to be used. mix and the desired size of the thermoplastic material particles.
- the mixture, before being cooled according to step b), can be extruded through a die to be shaped rod, wire, film in a conventional manner and known to those skilled in the art.
- Step b) is to cool the mixture to solidify at least the thermoplastic polymer. This cooling can be carried out conventionally using air or water
- thermoplastic polymer particles from the cooled mixture can be carried out according to different methods.
- a first method consists in the application of a mechanical force, such as friction, shear, torsion, necessary to cause this disintegration;
- the disintegration occurs instantaneously when the cooled mixture is introduced into a liquid such as water, for example.
- the liquid is advantageously a solvent of additive A and compound B.
- the thermoplastic polymer powder will comprise a smaller amount of impurities, additive A and compound B.
- steps b) and c) are performed simultaneously.
- the mixture can be introduced after extrusion through a die directly into a reactor comprising a solvent of additive A and compound B and a non-solvent of polymer P.
- the polymer particles P are optionally isolated from the solvent solution.
- Isolation can be achieved by any means for separating from a liquid phase, a solid phase in suspension. The isolation may consist for example of filtration, decantation, centrifugation, atomization.
- the isolation can be carried out for example by atomization to recover a powder comprising elementary particles of size equivalent to those present in the dispersion and / or aggregates of particles. These aggregates are generally easily redispersible in an aqueous medium such as water or broken by applying vibrations to the powder. Other means of removing water or recovering the powder can be used such as filtration or centrifugation and then drying the filter cake.
- the polymer particles P thus obtained can be washed and dried.
- the process of the invention makes it possible to obtain particles with a controlled geometry, in particular by adjusting the stirring during step a), the nature of compounds A and / or B, the temperature and the concentration of the various components of the mixture. .
- thermoplastic material powders that can be obtained by the method of the invention.
- the particles obtained according to the process of the invention are spherical particles.
- spherical particle is meant a particle of substantially spherical shape.
- the average particle diameter desired according to the process of the invention is advantageously between 0.1 and 800 ⁇ m.
- the desired diameter varies depending on the fields of application of the powders.
- the particle size of the powders of the invention is controlled, the particle size distribution is generally uni modal.
- diameter is meant the value of the modal peak of the uni modal distribution of the particle size.
- the size distribution of the particles is generally determined by laser granulometry according to a method known to those skilled in the art.
- the particles may also be of regular or irregular polyhedral shape. These particles constituting the powder of thermoplastic material generally have a pore volume equal to or close to 0 cm 3 / g because the particles have no porosity.
- Additive A hydrophilic star-shaped polyamide-polyalkylene oxide copolymer produced in the following manner:
- Compound B1 Ethylene polyoxide with a molecular weight of 400 g / mole
- Compound B2 Ethylene oxide with a molecular weight of 1,500 g / mole
- Compound B3 Ethylene oxide with a molecular weight of 12,000 g / mole
- a Polymer P granulate is introduced into a Prism type 24D twin screw extruder using a volumetric feed and a mixture of pellets of additive A and compound B (B1, B2 or B3) using of a weight diet.
- the flow rates of the two feeders are adjusted so as to be able to vary the concentration of additive A and compound B in the mixture with the thermoplastic polymer P.
- the mixtures are extruded at a fixed flow rate between 1 and 2.2 kg / hour.
- the temperatures of the different ranges of the extruder are between 275 and 295 °.
- the speed is set at 200 rpm.
- the recorded pressure is between 10 and 13 bar.
- the rods obtained are quenched at the outlet of the die by a stream of water, collected in a metal basket, drained and then dried. The rushes collected are then dispersed in water by simple mechanical stirring.
- the dispersion thus obtained is sieved with a 200 .mu.m sieve to remove large solid impurities such as non-dispersible rods.
- the weight recovery efficiencies of thermoplastic polymer P after sieving are greater than 90%.
- the particle size distribution of the particles contained in the dispersion is measured using a device called MasterSizer 2000 marketed by Malvern Instruments. This distribution, expressed in volume, obtained after application of Ultrasound, is unimodal and the value reported in the tables below corresponds to the value of the modal peak.
- powders having varying particle sizes are produced, and for each particle size the concentrations of additive A and of compound are varied.
- Figure 1 corresponding to Examples 1 to 35, illustrates the linear relationship between the mass ratios R1 and R2 for a given particle size.
- powders are produced with compounds B1 and B3 (see Table 3 below).
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
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Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602007006461T DE602007006461D1 (de) | 2006-04-10 | 2007-04-03 | Verfahren zur herstellung von partikeln auf der basis von thermoplastischem polymer |
JP2009504690A JP5417168B2 (ja) | 2006-04-10 | 2007-04-03 | 熱可塑性ポリマーをベースとする粒子の製造方法及び得られる粉体 |
EP07727722A EP2004751B1 (fr) | 2006-04-10 | 2007-04-03 | Procede de preparation de particules a base de polymere thermoplastique |
AT07727722T ATE467661T1 (de) | 2006-04-10 | 2007-04-03 | Verfahren zur herstellung von partikeln auf der basis von thermoplastischem polymer |
BRPI0709413-2A BRPI0709413A2 (pt) | 2006-04-10 | 2007-04-03 | processo de fabricação de pó de material termoplástico p e pó de materia termoplástico p |
US12/226,226 US8444886B2 (en) | 2006-04-10 | 2007-04-03 | Preparation of thermoplastic polymer particles having controlled geometry and powders obtained therefrom |
CN2007800131025A CN101421355B (zh) | 2006-04-10 | 2007-04-03 | 制备基于热塑性聚合物的颗粒的方法和由此获得的粉末 |
CA002648596A CA2648596A1 (fr) | 2006-04-10 | 2007-04-03 | Procede de preparation de particules a base de polymere thermoplastique et poudre ainsi obtenue |
PL07727722T PL2004751T3 (pl) | 2006-04-10 | 2007-04-03 | Sposób wytwarzania cząstek na bazie polimeru termoplastycznego |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0603142 | 2006-04-10 | ||
FR0603142A FR2899591B1 (fr) | 2006-04-10 | 2006-04-10 | Procede de preparation de particules a base de polymere thermoplastique et poudre ainsi obtenue |
Publications (1)
Publication Number | Publication Date |
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WO2007115977A1 true WO2007115977A1 (fr) | 2007-10-18 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/053251 WO2007115977A1 (fr) | 2006-04-10 | 2007-04-03 | Procede de preparation de particules a base de polymere thermoplastique et poudre ainsi obtenue |
Country Status (14)
Country | Link |
---|---|
US (1) | US8444886B2 (fr) |
EP (1) | EP2004751B1 (fr) |
JP (1) | JP5417168B2 (fr) |
KR (1) | KR101007531B1 (fr) |
CN (1) | CN101421355B (fr) |
AT (1) | ATE467661T1 (fr) |
BR (1) | BRPI0709413A2 (fr) |
CA (1) | CA2648596A1 (fr) |
DE (1) | DE602007006461D1 (fr) |
ES (1) | ES2341587T3 (fr) |
FR (1) | FR2899591B1 (fr) |
PL (1) | PL2004751T3 (fr) |
RU (1) | RU2423399C2 (fr) |
WO (1) | WO2007115977A1 (fr) |
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WO2012076528A1 (fr) | 2010-12-10 | 2012-06-14 | Rhodia Operations | Realisation d'article par fusion selective de couches de poudre de polymere |
WO2015109143A1 (fr) | 2014-01-17 | 2015-07-23 | Lubrizol Advanced Materials, Inc. | Procédés d'utilisation de polyuréthanes thermoplastiques dans le frittage laser sélectif, systèmes et articles associés |
US9512285B2 (en) | 2012-06-12 | 2016-12-06 | Rhodia Operations | Method for heat-treating powders |
EP2352636B1 (fr) | 2008-12-01 | 2018-05-30 | Rhodia Opérations | Realisation d'article par fusion selective de couches de poudre de polymere |
WO2018115767A1 (fr) | 2016-12-22 | 2018-06-28 | Setup Performance | Poudre de particules spheriques de polyamide reticulable, procede de preparation et utilisation avec la technique de frittage par laser selectif |
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-
2007
- 2007-04-03 WO PCT/EP2007/053251 patent/WO2007115977A1/fr active Application Filing
- 2007-04-03 US US12/226,226 patent/US8444886B2/en not_active Expired - Fee Related
- 2007-04-03 JP JP2009504690A patent/JP5417168B2/ja not_active Expired - Fee Related
- 2007-04-03 AT AT07727722T patent/ATE467661T1/de not_active IP Right Cessation
- 2007-04-03 BR BRPI0709413-2A patent/BRPI0709413A2/pt not_active IP Right Cessation
- 2007-04-03 DE DE602007006461T patent/DE602007006461D1/de active Active
- 2007-04-03 KR KR1020087024803A patent/KR101007531B1/ko not_active IP Right Cessation
- 2007-04-03 ES ES07727722T patent/ES2341587T3/es active Active
- 2007-04-03 CN CN2007800131025A patent/CN101421355B/zh not_active Expired - Fee Related
- 2007-04-03 PL PL07727722T patent/PL2004751T3/pl unknown
- 2007-04-03 EP EP07727722A patent/EP2004751B1/fr not_active Not-in-force
- 2007-04-03 CA CA002648596A patent/CA2648596A1/fr not_active Abandoned
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2037876A1 (fr) * | 2006-07-11 | 2009-03-25 | Rhodia Opérations | Compositions cosmetiques comprenant une poudre en materiau thermoplastique |
EP2352636B1 (fr) | 2008-12-01 | 2018-05-30 | Rhodia Opérations | Realisation d'article par fusion selective de couches de poudre de polymere |
WO2012076528A1 (fr) | 2010-12-10 | 2012-06-14 | Rhodia Operations | Realisation d'article par fusion selective de couches de poudre de polymere |
US9321192B2 (en) | 2010-12-10 | 2016-04-26 | Rhodia Operations | Production of an article by selective fusion of polymer powder layers |
US9512285B2 (en) | 2012-06-12 | 2016-12-06 | Rhodia Operations | Method for heat-treating powders |
WO2015109143A1 (fr) | 2014-01-17 | 2015-07-23 | Lubrizol Advanced Materials, Inc. | Procédés d'utilisation de polyuréthanes thermoplastiques dans le frittage laser sélectif, systèmes et articles associés |
EP3798267A1 (fr) | 2014-01-17 | 2021-03-31 | Lubrizol Advanced Materials, Inc. | Procédés d'utilisation de polyuréthanes thermoplastiques dans le frittage laser sélectif, systèmes et articles associés |
WO2018115767A1 (fr) | 2016-12-22 | 2018-06-28 | Setup Performance | Poudre de particules spheriques de polyamide reticulable, procede de preparation et utilisation avec la technique de frittage par laser selectif |
US11236242B2 (en) | 2016-12-22 | 2022-02-01 | SETUP Performance SAS | Powder of spherical crosslinkable polyamide particles, preparation process and use with the selective laser sintering technique |
US11891528B2 (en) | 2016-12-22 | 2024-02-06 | SETUP Performance SAS | Powder of spherical crosslinkable polyamide particles, preparation process and use with the selective laser sintering technique |
Also Published As
Publication number | Publication date |
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JP5417168B2 (ja) | 2014-02-12 |
KR20080108536A (ko) | 2008-12-15 |
CN101421355A (zh) | 2009-04-29 |
KR101007531B1 (ko) | 2011-01-14 |
CA2648596A1 (fr) | 2007-10-18 |
RU2423399C2 (ru) | 2011-07-10 |
ATE467661T1 (de) | 2010-05-15 |
EP2004751A1 (fr) | 2008-12-24 |
US8444886B2 (en) | 2013-05-21 |
BRPI0709413A2 (pt) | 2011-07-12 |
DE602007006461D1 (de) | 2010-06-24 |
FR2899591B1 (fr) | 2008-05-23 |
FR2899591A1 (fr) | 2007-10-12 |
ES2341587T3 (es) | 2010-06-22 |
JP2009533507A (ja) | 2009-09-17 |
PL2004751T3 (pl) | 2010-10-29 |
CN101421355B (zh) | 2011-12-14 |
RU2008144184A (ru) | 2010-05-20 |
US20100009189A1 (en) | 2010-01-14 |
EP2004751B1 (fr) | 2010-05-12 |
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