EP3710255A1 - Composition pour procédé de fabrication additive - Google Patents

Composition pour procédé de fabrication additive

Info

Publication number
EP3710255A1
EP3710255A1 EP18804556.1A EP18804556A EP3710255A1 EP 3710255 A1 EP3710255 A1 EP 3710255A1 EP 18804556 A EP18804556 A EP 18804556A EP 3710255 A1 EP3710255 A1 EP 3710255A1
Authority
EP
European Patent Office
Prior art keywords
composition
polymer
additive
composition according
polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18804556.1A
Other languages
German (de)
English (en)
Inventor
Stoyan Frangov
Andreas Pfister
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EOS GmbH
Original Assignee
EOS GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EOS GmbH filed Critical EOS GmbH
Publication of EP3710255A1 publication Critical patent/EP3710255A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
    • 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
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • 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
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
    • C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • 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
    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • 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
    • 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
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • 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
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/04—Polysulfides

Definitions

  • the present invention relates to a composition comprising at least one polymer, wherein the composition contains at least one additive, wherein the additive has a content of at most 2 wt .-% of the composition. Furthermore, the present invention relates to a process for the preparation of the composition according to the invention and to a component comprising a composition according to the invention and the use of the composition according to the invention.
  • Additive manufacturing processes for the production of prototypes and the industrial production of components based on powdered materials enable the manufacture of plastic objects and are becoming increasingly important.
  • the desired structures are produced in layers by selective melting and solidification or by applying a binder and / or adhesive.
  • the process is also referred to as additive manufacturing, digital fabrication, or three-dimensional (3D) printing.
  • additive manufacturing is often replaced by “additive manufacturing” or “rapid technology”.
  • Additive manufacturing processes which use a powdery material include, for example, sintering, melting or bonding by binders.
  • the crystallization of the polymer begins during cooling.
  • the process of crystallization is always associated with geometric changes, shrinkage and often distortion of the 3D component.
  • a Retardation of the crystallization ie a lowering of the temperature at which the polymer crystallizes, is also advantageous in order to achieve a layer connection in the melt with the underlying component layers, since interdiffusion between the layers can take place only in the melt.
  • 3D components in the final state tend to delaminate and lose strength.
  • the installation space temperature during the production process should thus be conducted as far as possible so that the crystallization of the polymer during the building process is suppressed as long as possible. If this fails, process errors such as distortion occur during production.
  • the installation space temperature In the production of 3D components, on the one hand, the installation space temperature must be above the crystallization temperature of the respective polymer, on the other hand, however, the temperature must necessarily be below the melting point, since otherwise the powder cake would melt in the installation space.
  • the temperature range between the crystallization temperature (TK) and the melting temperature (TM) is called the process window or the sintered window of the polymer. If crystallization and melting of a polymer overlap on the temperature axis to a significant extent, this polymer is highly likely not accessible to the process, d. H. it does not have a sufficient process window.
  • additives often lead to undesirable properties, such as an unfavorable melting behavior by reducing the process window, d. H. the temperature range at which the polymer system can be processed.
  • the crystallization temperature of the polymer for example by the addition of flow aids or anti-agglomeration agents, unfavorably increase, which in turn reduces the process window.
  • composition according to claim 1 which comprises at least one polymer and at least one additive. Furthermore, the object is achieved by a method for producing the composition according to claim 16, by a method for producing a component according to claim 17 and by a use of the composition according to the invention according to claim 20.
  • the present invention therefore relates to a composition, in particular as a building material for an aforementioned additive manufacturing, comprising
  • polymer is in the form of polymer particles and wherein the polymer is selected from at least one thermoplastic polymer, and
  • the at least one additive has a content of at least 0.005 wt .-%, preferably of at least 0.01 wt .-%, particularly preferably of at least 0.05 wt .-%, in particular of at least 0.075 wt .-%, particularly preferably of has at least 0.1 wt .-%, most preferably of at least 0.2 wt .-%, of the composition,
  • the additive has a content of at most 2 wt .-%, preferably of at most 1, 5 wt .-%, particularly preferably of at most 1 wt .-%, in particular of at most 0.7 wt .-%, particularly preferably of at most 0 5% by weight of the composition.
  • a composition according to the invention comprises a polymer or a polymer system which is selected from a thermoplastic polymer and an additive.
  • an additive is understood as meaning a substance which may be, in particular, an amorphous and / or partially crystalline and / or crystalline polymer, a polyol, a surfactant and / or a protective colloid, which or which make it possible to lower the crystallization temperature and / or enthalpy of crystallization of the thermoplastic polymer even in very low concentrations of up to 2% by weight.
  • the enthalpy of crystallization can be reduced by a percentage which is relatively higher than the concentration of the additive.
  • the ratio of the enthalpy of crystallization to the concentration of the additive is preferably about 10%, preferably about 20%, particularly preferably about 50% and in particular about 100% higher.
  • the additive is preferably a partially crystalline polymer, a partially crystalline polyol and / or a partially crystalline surfactant and / or a partially crystalline protective colloid.
  • the additive is soluble in water at room temperature.
  • an additive has a solubility of at least about 30 g / L of water.
  • the composition according to the invention is in the form of a powder.
  • the composition has a content of the additive of at least 0.005 wt .-%, preferably of at least 0.01 wt .-%, particularly preferably of at least 0.05 wt .-%, in particular of at least 0.075 wt .-%, particularly preferably of at least 0.1% by weight, very particularly preferably of at least 0.2% by weight of the composition, and / or the composition has a content of the additive of at most 2% by weight, preferably of at most 1, 5 wt .-%, particularly preferably of at most 1 wt .-%, in particular of at most 0.7 wt .-%, particularly preferably of at most 0.5 wt .-% to.
  • the additive is preferably bound to the polymer or the polymer particles, for example, on the surface or deposited.
  • such a proportion of an additive in the composition or the polymer can bring about a lowering of the crystallization temperature and / or an increase in the difference DTK / TM of the crystallization temperature (TK) and the melting temperature (TM), ie an expansion of the process window.
  • TK crystallization temperature
  • TM melting temperature
  • Under Crystallization temperature and melting temperature is to be understood as the peak temperature, as defined in DIN EN ISO 11357.
  • the degree of crystallization can be measured by various analytical methods, such as DSC.
  • the degree of crystallinity is calculated via the enthalpy of fusion [J / g] (in comparison to a polymer which is theoretically 100% crystalline).
  • the term enthalpy of fusion is understood to mean the amount of energy required to melt a substance sample at its melting point at constant pressure (isobaric), ie to transfer it from the solid to the liquid state of aggregation.
  • too high a content of the additive leads to disadvantageous adhesion and / or caking effects of the polymer particles, as a result of which the flowability and the process capability of the particles are greatly impaired.
  • a content of at most 2% by weight of the additive in the composition according to the invention can effectively prevent sticking and / or caking effects and at the same time advantageously improve the pouring properties.
  • composition according to the invention ensures a homogeneous powder structure, so that in this way an improved flowability or flowability and thus in the course of additive manufacturing processes a uniform powder introduction is made possible.
  • a good flowability of a bulk material is given when the bulk material can be easily made to flow.
  • the most important parameter for this is the flowability, ie the extent of the free mobility of the bulk material. Under a polymer or a polymer system is used in the present
  • Patent application understood at least one homo- and / or a heteropolymer, which is made up of several monomers. While homopolymers have a covalent linking of identical monomers, heteropolymers (also called copolymers) are composed of covalent linkages of different monomers.
  • a polymer system according to the present invention may comprise both a mixture of the abovementioned homo- and / or heteropolymers or else more than one polymer system. Such a mixture is also referred to in the present patent application as a polymer blend.
  • Heteropolymers in the context of the present invention can be selected from random copolymers in which the distribution of the two monomers in the chain is random, from gradient copolymers which are in principle similar to the random copolymers, but in which the proportion of one monomer in the course of the chain and the other decreases, from alternating copolymers in which the monomers alternately alternate, from block copolymers or segment copolymers consisting of longer sequences or blocks of each monomer, and from
  • Graft copolymers in which blocks of one monomer are grafted onto the backbone of another monomer.
  • the composition of the invention can be advantageously used for additive manufacturing processes.
  • Additive manufacturing processes include in particular processes which are suitable for the production of prototypes (rapid prototyping) and components (rapid manufacturing), preferably from the group of powder bed-based processes comprising laser sintering, high-speed sintering, multi-jet fusion, binder jetting selective mask sintering or selective laser melting.
  • the composition of the invention is intended for use in laser sintering.
  • laser sintering is synonymous with the term “selective laser sintering” to understand; the latter is just the older name.
  • the present invention relates to a method for producing a composition according to the invention, the method comprising the following steps:
  • composition has a content of the at least one additive of at least 0.005 wt .-%, preferably of at least 0.01 wt .-%, particularly preferably of at least 0.05 wt .-%, in particular of at least 0.075 wt .-%, in particular preferably of at least 0.1% by weight, most preferably of at least 0.2% by weight of the composition,
  • composition has a content of the additive of at most 2 wt .-%, preferably of at most 1, 5 wt .-%, particularly preferably of at most 1 wt .-%, in particular of at most 0.7 wt .-%, particularly preferably of has at most 0.5 wt .-%.
  • providing is meant both an on-site production and a delivery of a polymer or a polymer system.
  • a process of mixing, admixing, blending or compounding can take place in the course of an extrusion in the extruder, in the kneader, in the disperser and / or in the stirrer and optionally comprises process operations such as melting, dispersing, etc.
  • a mixing process takes place in the extruder, particularly preferably by melt extrusion.
  • a mixing operation of the polymer with an additive, preferably in the melt can take place in a kneader.
  • it is preferred that the mixing process takes place in an extruder, in particular by melt extrusion.
  • the removal or separation of the additive preferably takes place by centrifuging and / or filtering.
  • a packaging process advantageously takes place in the absence of moisture.
  • a composition produced by the process according to the invention is advantageously used as a solidifiable powder material in a process for the layered production of a three-dimensional object of powdery material, successive layers of the object to be formed from this solidifiable powder material successively at corresponding or predetermined locations by the entry of energy, preferably of electromagnetic radiation, in particular by the entry of laser light, solidified.
  • the present invention also includes a composition, in particular for laser sintering methods, which is obtainable or obtainable by the method described above.
  • composition according to the invention for producing a component, in particular a three-dimensional object, by layering and selectively solidifying a building material, preferably a powder is used.
  • solidifying is understood to mean at least partial melting or melting with subsequent solidification or resolidification of the building material.
  • an advantageous method for producing a component has at least the following steps:
  • build-up material is understood as meaning a powder or a solidifiable powder material, which by means of additive manufacturing processes, preferably by means of powder bed-based method, in particular by means of laser sintering or laser melting, can be solidified into moldings or 3D objects.
  • building material in particular the composition of the invention is suitable.
  • the construction field used here is a plane which is located on a carrier within a machine for additive production at a specific distance from an irradiation unit mounted above it, which is suitable for solidifying the building material.
  • the building material On the support, the building material is positioned so that its uppermost layer coincides with the plane which is to be solidified.
  • the carrier can be adjusted so that each newly applied layer of the building material has the same distance to the irradiation unit, preferably a laser, and can be solidified in this way by the action of the irradiation unit.
  • a component, in particular a 3D object, which has been produced from the composition according to the invention can have an advantageous tensile strength and elongation at break.
  • the tensile strength characterizes the maximum mechanical tensile stress that can occur in the material.
  • the determination of the tensile strength is known to the person skilled in the art and can be determined, for example, according to DIN EN ISO 527.
  • the elongation at break marks the deformation capability of a material in the plastic range (also called ductility) until it breaks and can be determined, for example, by means of DIN EN ISO 527-2.
  • a component which has been produced from the composition according to the invention has improved dimensional stability and / or lower component distortion.
  • Dimensional accuracy is understood to mean that the actual dimensions of a workpiece lie within the agreed permissible deviation or tolerance from the specified nominal size. In the laser sintering process, this dimensional accuracy can preferably be determined on the basis of the component distortion. Further, the term refers to the durability of a material, for example, in terms of elongation and shrinkage. Frequent causes of dimensional changes are, for example, temperature, compressive or tensile forces, aging and moisture. Also, the present invention includes a component obtainable by the method described above. A use of the composition according to the invention can be carried out both in rapid prototyping and in rapid manufacturing.
  • additive manufacturing processes preferably from the group of powder bed-based processes comprising laser sintering, high-speed sintering, binder jetting, selective mask sintering, selective laser melting, in particular for use for laser sintering, are used, in which preferably Three-dimensional objects are formed in layers by selectively projecting a laser beam having a desired energy onto a powder bed of powdered materials. Prototypes or production parts can be produced by this process in a time- and cost-efficient manner.
  • the present invention comprises a composition as a solidifiable powder material in a process for the layered production of a three-dimensional object of powdered material, in which successive layers of the object to be formed from this solidifiable powder material successively solidified at corresponding points by the entry of energy, preferably by the entry of electromagnetic radiation, in particular by the entry of laser light.
  • the composition according to the invention comprises at least one additive.
  • such an additive is immiscible with the at least one thermoplastic polymer.
  • the at least one additive is selected from a semi-crystalline polymer (such as polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone), a semi-crystalline cellulose ether (such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose) and / or a semi-crystalline polyacrylate, a semi-crystalline starch, a semi-crystalline protein , a semi-crystalline alginate, a semi-crystalline pectin and / or a semi-crystalline gelatin.
  • a semi-crystalline polymer such as polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone
  • a semi-crystalline cellulose ether such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose
  • a semi-crystalline polyacrylate such as methylcellulose, hydroxyeth
  • the additive is selected from at least one polyol, in particular a partially crystalline polyol.
  • a polyol is particularly preferably selected from at least one partially crystalline polyethylene glycol and / or from at least one partially crystalline polyethylene oxide and / or from at least one partially crystalline polyvinyl alcohol, more preferably from at least one partially crystalline polyethylene glycol.
  • a polyethylene glycol comprises a mixture of at least two partially crystalline polyethylene glycols, which preferably have a different molecular weight. The use of polyethylene glycols having different molecular weights advantageously makes it possible to set a suitable viscosity.
  • the at least one preferably partially crystalline polyethylene glycol preferably has a molecular weight of at least 10,000 D, preferably of at least 15,000 D, particularly preferably of at least 20,000 D and / or of at most 500,000 D, preferably of at most 250,000 D, particularly preferably of at most 100 000 D, in particular of at most 40 000 D, in particular preferably of at most 35 000 D, on.
  • a particularly preferred additive comprises a mixture of at least two partially crystalline polyethylene glycols with a polyethylene glycol having a Molecular weight of 20,000 D and a polyethylene glycol having a molecular weight of 500,000 D or else a mixture of a polyethylene glycol having a molecular weight of 35,000 D and a polyethylene glycol having a molecular weight of 100,000 D, in particular a mixture of a polyethylene glycol having a molecular weight of 20,000 D and a polyethylene glycol having a molecular weight of 35,000 D.
  • the additive is selected from a surfactant such as at least one nonionic organic surfactant and / or polymeric surfactant.
  • the surfactant is selected from sodium dodecyl sulfate.
  • a preferred surfactant is present in partially crystalline form.
  • an advantageous composition comprises more than one additive
  • the proportions of the individual additives add up in such a way that their sum gives the proportion according to the invention as specified above.
  • an advantageous composition has a crystallization temperature which is at least 2 ° C., preferably at least 3 ° C., more preferably at least 4 ° C., in particular at least 5 ° C., in comparison to the thermoplastic polymer without additive and / or a difference DTK / TM of the crystallization temperature (TK) and the melting temperature (TM), which increases by at least 1 ° C, preferably by at least 3 ° C, more preferably by at least 5 ° C.
  • TK crystallization temperature
  • TM melting temperature
  • Composition has a melting enthalpy of at least 20 J / g, preferably of at least 40 J / g, in particular of at least 60 J / g on. At most, an advantageous composition has a melting enthalpy of up to 150 J / g, preferably of up to 140 J / g, in particular of up to 130 J / g. Such an advantageous composition allows a better delimitation of the component of non-sintered powder, as this less fused to the component powder particles are melted. Furthermore, such a favorable melting enthalpy can bring about a higher building temperature and thus an extended process window.
  • an advantageous composition comprises a thermoplastic polymer which is selected from at least one polyetherimide, polycarbonate, polysulfone, polyphenylene sulfone, polyphenylene oxide, polyethersulfone, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylate copolymer (ASA ), Polyvinyl chloride, polyacrylate, polyester, polyamide, polypropylene, polyethylene, polyaryletherketone, polyether, polyurethane, polyimide, polyamideimide, polyolefin, polyarylene sulfide and copolymers thereof.
  • a thermoplastic polymer which is selected from at least one polyetherimide, polycarbonate, polysulfone, polyphenylene sulfone, polyphenylene oxide, polyethersulfone, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-s
  • the polymer particularly preferably comprises a polyamide and / or a polypropylene.
  • the at least one polymer is preferably selected from at least one homopolymer and / or heteropolymer and / or from a polymer blend, wherein the at least one homo- and / or heteropolymer and / or polymer blend particularly preferably a partially crystalline homo- and / or heteropolymer and / or amorphous homo- and / or heteropolymer.
  • the at least one homo- and / or heteropolymer and / or polymer blend is selected from at least one semicrystalline polymer or a partially crystalline polymer blend of at least one semicrystalline polymer and at least one further semicrystalline polymer or a partially crystalline polymer blend of at least one semicrystalline polymer and an amorphous polymer.
  • partially crystalline in the present case means a substance which contains both crystalline and amorphous regions.
  • a polymer is considered substantially amorphous if its degree of crystallinity in the solid state is 5% by weight or less, more preferably 2% by weight or less.
  • a polymer is considered to be substantially amorphous in particular if no melting point can be determined by means of differential scanning calorimetry (DSC) and / or the enthalpy of fusion is below 1 J / g.
  • a partially crystalline substance can comprise up to 95% by weight, preferably up to 99% by weight, in particular up to 99.9% by weight, of crystalline regions.
  • the heteropolymer or copolymer preferably has at least two different repeat units and / or at least one polymer blend based on the abovementioned polymers and copolymers.
  • a heteropolymer or copolymer and / or polymer blend is partially crystalline.
  • a composition according to the invention preferably comprises a polymer and / or a copolymer and / or a polymer blend having a melting temperature of at least about 50 ° C, preferably of at least about 100 ° C.
  • the melting temperature of the polymer and / or the copolymer and / or the polymer blend is at most about 400 ° C, preferably at most about 350 ° C.
  • the term "melting temperature” is understood to mean the temperature or the temperature range at which a substance, preferably a polymer or copolymer or polymer blend, passes from the solid to the liquid state of aggregation.
  • the composition according to the invention comprises a polymer or a polymer system, which is preferably selected from at least one polypropylene and / or a polyamide.
  • Polypropylene (PP, syn polypropene, poly (1-methylethylene)) is a thermoplastic polymer prepared by chain polymerization of propene. It belongs to the group of polyolefins and is generally semi-crystalline and nonpolar.
  • the at least one polypropylene can be present in atactic, syndiotactic and / or isotactic form.
  • atactic polypropylene the methyl group is random, in syndiotactic polypropylene alternating (alternating) and evenly aligned in isotactic polypropylene. This can affect the crystallinity (amorphous or semi-crystalline) and the thermal properties (such as the glass transition temperature and the melting temperature).
  • the tacticity is usually indicated by means of the isotactic index (according to DIN 16774) in percent.
  • the polypropylene is selected from an isotactic polypropylene.
  • the at least one preferred polypropylene may be selected from an isotactic polypropylene and / or its copolymers with polyethylene or with maleic anhydride.
  • the copolymer fraction of the polyethylene is particularly preferably up to 50% by weight, more preferably up to 30% by weight.
  • At least one polymer blend of polypropylene with at least one ethylene-vinyl acetate copolymer can be used.
  • Such a polymer blend advantageously has a higher impact strength, ie the ability to absorb impact energy and impact energy without breaking.
  • composition according to the invention comprises a polymer which is selected from a polypropylene, in particular from an isotactic polypropylene
  • the content of the additive in this composition is at least 0.005 wt.%, Preferably at least 0.01 wt.%, Particularly preferred at least 0.05% by weight, in particular at least 0.075% by weight, particularly preferably at least
  • the polypropylene is selected from a polypropylene-polyethylene copolymer.
  • Polyamides are linear polymers with regularly repeating amide bonds along the main chain.
  • the amide group can be considered as the condensation product of a carboxylic acid and an amine.
  • the resulting bond is an amide bond, which is hydrolytically cleavable again.
  • polyamides is commonly used as a term for synthetic, technically usable thermoplastic polymers.
  • a composition according to the invention comprises a polymer selected from a polyamide
  • the content of the additive in the composition is preferably at least 0.005% by weight, more preferably at least 0.01% by weight and / or preferably at most 0 , 9 wt .-%, more preferably at most 0.8 wt .-%, in particular at most 0.7 wt .-%.
  • the at least one polyamide is selected from polyamide 6, polyamide 1 1, polyamide 12, polyamide 46, polyamide 66, polyamide 1010, polyamide 1012, polyamide 1 112, Polyamide 1212, polyamides PA6T / 6I, poly-m-xylylene adipamide (PA MXD6), polyamides 6 / 6T, polyamides PA6T / 66, PA4T / 46 and / or platamide M1757.
  • polyamide 6 polyamide 1 1, polyamide 12, polyamide 46, polyamide 66, polyamide 1010, polyamide 1012, polyamide 1 112, Polyamide 1212, polyamides PA6T / 6I, poly-m-xylylene adipamide (PA MXD6), polyamides 6 / 6T, polyamides PA6T / 66, PA4T / 46 and / or platamide M1757.
  • thermoplastic polymer is selected from at least one polyaryletherketone selected from the group of polyether ketone ketone (PEKK) and / or from the group of polyetheretherketone-polyetherdiphenyletherketone (PEEK-PEDEK).
  • PEKK polyether ketone ketone
  • PEEK-PEDEK polyetheretherketone-polyetherdiphenyletherketone
  • a further preferred embodiment comprises a polyether-ether-ketone-polyether-diphenyl-ether-ketone (PEEK-PEDEK) with the following repeating units:
  • the said polyetheretherketone-polyetherdiphenyletherketone polymer may have a mole fraction of at least 68 mol%, preferably of at least 71 mol%, of the repeat unit A.
  • Particularly preferred polyether-ether-ketone-polyether-diphenyl-ether-ketone polymers have a molar fraction of at least 71 mol%, or, more preferably, of at least 74 mol%, of the repeat unit A.
  • Said polyetheretherketone-polyetherdiphenyletherketone polymer preferably has a molar fraction of less than 90 mol%, more preferably of 82 mol% or less of the repeating unit A.
  • the said polymer further comprises a preferred mole fraction of at least 68 mole%, more preferably at least 70 mole%, especially at least 72 mole%, of repeat unit A.
  • the polyetheretherketone Polyetherdiphenyletherketon polymer a preferred mole fraction of 82 mol%, more preferably of at most 80 mol%, in particular of at most 77 mol%, of the repeat unit A.
  • the ratio of repeat unit A to repeat unit B is preferably at least 65:35 and / or at most 95:5.
  • the number of repeat units A and B may preferably be at least 10 and / or at most 2,000.
  • the molecular weight (MW) of such a polyetheretherketone-Polyetherdiphenyletherketons is at least 10,000 D (Dalton, syn. Da), more preferably at least 15 000 D and / or at most 200 000 D, in particular at least 15 000 D and / or at most 100,000 D.
  • the weight average molecular weight of such a preferred polymer is preferably at least 20,000 D, more preferably at least 30,000 D and / or at most 500,000 D, in particular at least 30,000 D and / or at most 200,000 D.
  • molecular weight is used in the present invention, it is the number average molecular weight. Inasmuch as the weight average molecular weight is referred to, this is explicitly mentioned.
  • a further preferred composition comprises a polyether ketone ketone having the following repeating units:
  • the ratio of 1, 4-phenylene units in the repeat unit A to 1, 3-phenylene units in the repeat unit B is preferably 90:10 to 10:90, more preferably 70:30 to 10:90, in particular at
  • the number ni or n 2 of the repeat unit A or repeat unit B can preferably be at least 10 and / or at most 2,000.
  • the molecular weight of such a polyether ketone ketone is at least 10,000 D, more preferably at least 15,000 D and / or at most 200,000 D, in particular at least 15,000 D and / or at most 100,000 D.
  • the weight average molecular weight of such is preferably at least 20,000 D, more preferably at least 30,000 D and / or at most 500,000 D, in particular at least 30,000 D and / or at most 200,000 D.
  • a preferred polyether ketone ketone polymer can be obtained, for example, under the trade name Kepstan 6000 series (eg Kepstan 6001, 6002, 6003 or 6004, Arkema, France).
  • the melting temperature of the at least one polyaryletherketone is up to 330 ° C, preferably up to 320 ° C, in particular up to 310 ° C. At least the melting temperature of the at least one polyaryletherketone is 250 ° C.
  • the glass transition temperature of the at least one polyaryletherketone is preferably at least 120 ° C., preferably at least 140 ° C., in particular at least 160 ° C.
  • the term "glass transition temperature” is understood to mean the temperature at which a polymer changes into a rubbery to viscous state. The determination of the glass transition temperature is known to the person skilled in the art and can be carried out, for example, by means of DSC in accordance with DIN EN ISO 11357.
  • the low melting temperature or glass transition temperature of the at least one polyaryl ether ketone advantageously allows a low processing temperature, in particular during laser sintering, as well as less aging or an improved refreshing factor of the composition.
  • the term "refresh factor” is understood to mean the ratio of new powder to old powder.
  • the refreshing factor is advantageously improved or the aging significantly reduced and therefore a loss of unused powder is markedly reduced, as a result of which the economic efficiency in the production of a shaped article from the advantageous composition is also significantly improved.
  • the thermoplastic polymer is selected from at least one polyetherimide.
  • the polyetherimide particularly preferably has repeating units according to the
  • the number n of repeating units according to formulas I, II and III is preferably at least 10 and / or up to at most 1000.
  • the molecular weight of such a polyetherimide is at least 10 000 D, more preferably at least 15 000 D and / or at most 200 000 D, in particular at least 15 000 D and / or at most 100 000 D.
  • the weight average molecular weight of such is preferably at least 20,000 D, more preferably at least 30,000 D and / or at most 500,000 D, in particular at least 30,000 D and / or at most 200,000 D.
  • a preferred polyetherimide according to formula I is for example available under the trade name Ultem ® 1000, Ultem ® 1010, and Ultem ® 1040 (Sabic, Germany).
  • a preferred polyetherimide of the formula II for example, under the trade name Ultem ® 5001 and Ultem ® 501 1 (Sabic, Germany).
  • a further preferred composition comprises a thermoplastic polymer which is selected from at least one polycarbonate. The polycarbonate particularly preferably has repeating units according to the
  • the number n of repeating units according to the formula IV is preferably at least 20 and / or up to a maximum of 2,000.
  • the molecular weight of such a polycarbonate is at least 10 000 D, more preferably at least 15 000 D and / or at most 200 000 D, in particular at least 15 000 D and / or at most 100 000 D.
  • the weight average molecular weight of such is preferably at least 20,000 D, more preferably at least 30,000 D and / or at most 500,000 D, in particular at least 30,000 D and / or at most 200,000 D.
  • a suitable for use as starting material is polycarbonate, for example, by the company Sabic under the tradename Lexan ® (z. B. "Lexan ® 143R") or company Covestro sold under the trade name Makrolon ®.
  • the thermoplastic polymer is selected from polyarylene sulfide.
  • the polyarylene sulfide comprises a polyphenylene sulfide having recurring units according to
  • the number n of repeating units according to the formula V is preferably at least 50 and / or up to at most 5,000.
  • the molecular weight of such polyphenylene sulfide is preferably at least 10,000 D, more preferably at least 15,000 D and / or at most 200,000 D, in particular at least 15,000 D and / or at most 100,000 D.
  • the weight average molecular weight of such a preferred polymer is preferably at least 20,000 D, more preferably at least 30,000 D and / or at most 500,000 D, especially at least 30 000 D and / or at most 200 000 D.
  • a preferred polyphenylene sulfide is available, for example, from Celanese (Germany) under the trade name Fortran® .
  • an advantageous composition may comprise a polymer blend comprising a polyaryletherketone polyetherimide, a polyaryletherketone-polyetherimide polycarbonate, a polyphenylene sulfide-polyetherimide and / or a polyetherimide-polycarbonate.
  • a polymer blend for example, by the company Sabic (Germany) under the name Ultem ® are based 9085th
  • a further preferred composition comprises a polymer blend comprising a polyaryletherketone-polyetherimide, preferably a polyetherketone ketone with a ratio of repeat unit A to repeat unit B of 60 to 40.
  • a preferred composition may comprise a polyetherimide which preferably contains the repeat units of the formula I.
  • a preferred composition may comprise a polymer blend comprising a polyphenylene sulfide polyetherimide, preferably a polyphenylene sulfide according to the formula V and a polyetherimide according to the formula I.
  • a preferred composition may comprise a polycarbonate, in particular with the repeating unit of the formula IV, and / or a polyphenylene sulfide, in particular with the repeating unit of the formula V.
  • an advantageous composition comprises at least one adjuvant, wherein the adjuvant is preferably selected from heat stabilizers, oxidation stabilizers, UV stabilizers, fillers, dyes, plasticizers, reinforcing fibers, IR absorbers, Si0 2 particles, antiagglomeration agents, carbon black particles, carbon fibers , Glass fibers, carbon nanotubes, mineral fibers (eg wollastonite), aramid fibers (especially Kevlar fibers), glass beads, mineral fillers, inorganic and / or organic pigments and / or flame retardants (in particular phosphate flame retardants such as ammonium polyphosphate and / or brominated flame retardants and / or other halogenated flame retardants and / or inorganic flame retardants such as magnesium
  • the content of an adjuvant in the composition according to the invention may preferably be at least about 0.01% by weight and / or at most about 90% by weight, preferably at least 0.01% by weight and / or at most 50 % By weight.
  • the content is preferably at least 0.01% by weight and / or at most 5% by weight, in particular at least 0.01% by weight and / or at most 2 wt .-%.
  • the content is preferably at least 0.01 wt .-% and / or at most 1 wt .-%, preferably at least 0.01 wt .-% and / or at most 0.5 wt. %, more preferably at least 0.02 wt .-% and / or at most 0.2 wt .-%, in particular at least 0.02 wt .-% and / or at most 0.1 wt .-%.
  • an advantageous embodiment comprises
  • Composition therefore at least one anti-agglomeration agent.
  • Antiagglomerating agent is a synonym for the term “anti-caking agent”.
  • An anti-agglomeration agent in the present patent application means a substance in the form of particles which can be deposited on and / or in the polymer particles.
  • attachment is understood to mean that particles of the anti-agglomeration agent are formed, for example, by electrostatic forces, chemical bonds (for example ionic and covalent bonds) and hydrogen bonds and / or magnetic forces and / or van der Waals forces with particles of the polymer or interact of the polymer system and so come into relative spatial proximity to each other so that particles of the polymer system advantageously not directly contact each other, but are separated from each other by particles of the anti-agglomeration agent.
  • the spatially separate polymer system particles thus generally build up little or no interaction with one another, so that the addition of antiagglomeration agents advantageously counteracts clumping of the composition.
  • an advantageous composition comprises at least one anti-agglomeration agent.
  • an anti-agglomeration agent can be selected from the group of metal soaps, preferably from a silica, stearate, tricalcium phosphate, calcium silicate, alumina, magnesia, magnesium carbonate, zinc oxide, or mixtures thereof.
  • a first anti-agglomeration agent comprises silica.
  • This can be produced by a wet-chemical precipitation process or by fumed silica.
  • the silicon dioxide is particularly preferably pyrogenic silicon dioxide.
  • a pyrogenic silicon dioxide in the present patent application is understood to mean silicon dioxide which has been prepared by known processes, for example by flame hydrolysis, by adding liquid tetrachlorosilane to the hydrogen flame.
  • silicon dioxide is also referred to as silica.
  • a composition according to the invention comprises a second anti-agglomeration agent and thus advantageously enables improved matching of the physical properties, for example with respect to the electrostatic, magnetic and / or van der Waals forces of the anti-agglomeration agents Polymer / e and thus improved processability of the composition, especially in laser sintering processes.
  • the second anti-agglomeration agent is also a silicon dioxide, in particular pyrogenic silicon dioxide.
  • a composition according to the invention may also have more than two anti-agglomeration agents.
  • a preferred proportion of the at least one anti-agglomeration agent is at most about 1% by weight, more preferably at most about 0.5% by weight, particularly preferably at most about 0.2% by weight, in particular at most about 0.15 wt .-%, more preferably at most about 0.1 wt .-%.
  • the proportion refers to the proportion of all anti-agglomeration agents contained in the advantageous composition.
  • At least one or the two or more anti-agglomeration agents can be treated with one or more different hydrophobicizing agents.
  • the anti-agglomeration agent has a hydrophobic surface.
  • Such hydrophobing can be carried out, for example, with a substance based on organosilanes.
  • the additive can advantageously prevent caking and thus aggregation of particles of the polymer system in the composition and counteracts the formation of cavities during the pouring, whereby the bulk density of the composition is advantageously increased.
  • the bulk density can be influenced by its particle size or particle diameter and particle properties.
  • bulk density is meant the ratio of the mass of a granular solid which has been compacted by pouring and not by, for example, pounding or shaking, to the occupied bulk volume.
  • the determination of the bulk density is known to the person skilled in the art and can be carried out, for example, according to DIN EN ISO 60: 2000-01.
  • a particularly advantageous composition has a bulk density of at least about 350 kg / m 3 and / or at most about 650 kg / m 3 .
  • the bulk density here refers to the composition according to the invention.
  • composition according to the invention can advantageously be used to obtain round particles.
  • round particles are produced by means of melt dispersion, which advantageously have good flow properties.
  • compositions used in laser sintering processes a corresponding particle size or particle size distribution, a suitable bulk density and a sufficient flowability of the powder material are of importance.
  • grain size describes the size of individual particles or grains in a total mixture.
  • the grain or particle size distribution has an influence on the material properties of a bulk material, ie the granular total mixture, which is present in a pourable form, for example in a powdery composition.
  • polymer systems have small particle sizes or particle diameters.
  • the polymer systems can also be modified during their production, which however often leads to agglomeration of the particles. If you pour such polymer systems in about a powder bed of a laser sintering system, clumps, ie inhomogeneous particle distributions, can form, which do not melt continuously, and as a result a shaped body of inhomogeneous material is obtained, the mechanical stability of which may be reduced. Finally, clumping occurring during pouring can impair the flowability and thus limit the meterability. For this reason, antiagglomeration agents (syn. Flow aids) are often added to such polymer systems, which accumulate on the particles of the polymer system and counteract lumps which may arise, for example, during bulk operations and / or during application in the powder bed.
  • the particles of an advantageous composition have a particle size distribution
  • - d 10 of at least 10 pm, preferably of at least 20 pm and / or of at most 50 pm, preferably of at most 40 pm
  • - d50 at least 25 pm and / or at most 100 pm, preferably at least 30 pm and / or at most 80 pm, more preferably at least 30 pm and / or at most 60 pm
  • d90 at least 50 pm and / or at most 150 pm, preferably at most 120pm
  • an advantageous composition has a distribution width (d90-d10) / d50 of at most 3, preferably of at most 2, particularly preferably of at most 1.5, in particular of at most 1.
  • a further preferred composition has a fines content, ie a proportion of particles having a particle size of less than 10 ⁇ m, of less than 10% by weight, preferably of less than 6% by weight, in particular of less than 4% by weight.
  • the polymer particles of the composition according to the invention preferably have a substantially spherical to lenticular design or form.
  • the polymer particles particularly preferably have a particularly advantageous composition a sphericity of at least about 0.7, preferably at least about 0.8, more preferably at least about 0.9, most preferably at least about 0.95.
  • the determination of the sphericity can be carried out, for example, with the aid of microscopy (according to DIN ISO 13322-1) and / or a measuring device of the type Camsizer XT (Retsch Technology, Germany) (according to DIN ISO 13322-2).
  • the particles of a composition according to the invention have the smallest possible surface area.
  • the surface can be determined, for example, by gas adsorption according to the principle of Brunauer, Emmet and Teller (BET); The standard used is DIN EN ISO 9277.
  • BET Brunauer, Emmet and Teller
  • the particle surface determined by this method is also called the BET surface.
  • the BET surface area of an advantageous composition is at least about 0.1 m 2 / g and / or at most about 6 m 2 / g.
  • an advantageous composition here comprises at least one polymer which is selected from polypropylene.
  • a preferred BET surface area in this case is at least about 0.5 m 2 / g and / or up to about 2 m 2 / g.
  • the polymer which is preferably selected from a polypropylene and / or a polyamide or their copolymers or blends with other polymers, in the form of granules, which preferably by melt compounding in an extruder or kneader of the polymer and Additive is provided.
  • the advantageous composition is prepared by melt dispersion, in particular using polypropylene and / or polyamide.
  • the production of a powder from the granules can finally be advantageously carried out by grinding granules or by fiber spinning and cutting of the fibers or by melt spraying.
  • a polypropylene granule a melt volume-flow ratio (MVR: melt volume flow rate) of at least about 2 cm 3/10 min and / or a maximum of about 70 cm 3/10 min; a polyamide granules preferably has an MVR of at least about 10 cm 3/10 min and / or at most about 40 cm 3/10 min.
  • MVR melt volume-flow ratio
  • Flow ratio serves to characterize the flow behavior of the thermoplastic polymer at a certain temperature and test load.
  • the determination of the MVR is known to the person skilled in the art and can be carried out, for example, in accordance with DIN ISO EN 1 133: 2011.
  • the measurement for a polypropylene granules is carried out at a temperature of 230 ° C with a test load of 2.16 kg; the measurement of a polyamide granules takes place at a temperature of 235 ° C with a test load of 2.16 kg.
  • the drying of the granulate before the MVR determination is carried out according to the manufacturer's instructions.
  • the predrying of powder is carried out for 30 minutes at 105 ° C under vacuum (100 mbar).
  • the polymer is mixed by dispersion, in particular by melt dispersion, wherein the melt dispersion is in the form of a flowable multiphase system comprising the at least one polymer and the preferred additive.
  • the step of dispersing is preferably carried out by melt dispersion in a dispersing device, preferably in an extruder.
  • a melt dispersion can take place in a kneader.
  • a further preferred method comprises cooling the dispersion. Cooling can be done by means of a conveyor belt or a calender (system of several tempered rollers arranged on top of each other).
  • the dispersion can be located in a water trough and / or cooled by a water / air cooling section, which can extend over a few meters, for example.
  • the separation of the polymer or of the polymer particles from the mixture or the dispersion takes place and optionally washing and drying of the separated polymer or of the polymer particles.
  • Separation of the components of the mixture or dispersion is preferably carried out by centrifugation and / or filtration. Drying of the solid component to obtain the dried composition may e.g. B. in an oven, for example in a vacuum dryer, done.
  • an additive to the composition according to the invention can be carried out.
  • an additive is selected from an anti-agglomeration agent.
  • an addition of the additive in particular an antiagglomerating agent, in a mixer.
  • an advantageous manufacturing method may provide for packaging the composition.
  • a packaging of a composition prepared by the process according to the invention, in particular sieved polymer particles, which are preferably in the form of a powder, is preferably carried out under exclusion of atmospheric moisture, so that a subsequent storage of the composition according to the invention can take place under reduced humidity to avoid, for example, caking effects, causing the
  • compositions according to the invention are for additive
  • the target environment for example the powder bed of the irradiation unit, in particular of the laser beam, is heated before it is used, so that the temperature of the powder starting material is close to its melting temperature and already a low energy input is sufficient to increase the total energy input to such an extent the particles coalesce or solidify.
  • energy-absorbing and / or energy-reflecting substances can furthermore be applied to the target environment of the irradiation unit, as is known, for example, from the processes of high-speed sintering or multi-jet fusion.
  • melting is meant the process in which the powder is melted during an additive manufacturing process, for example in the powder bed, by introducing energy, preferably by means of electromagnetic waves, in particular by laser beams, at least partially.
  • the composition according to the invention thereby ensures at least partial melting and production of process-safe molded articles with high mechanical stability and dimensional accuracy.
  • an advantageous composition has a tensile strength of at least about 5 MPa, preferably of at least about 25 MPa, in particular of at least about 50 MPa. At most, the preferred composition has a tensile strength of about 500 MPa, preferably at most about 350 MPa, more preferably at most about 250 MPa.
  • the values for the elongation at break of the preferred composition are at least about 1%, particularly preferably at least about 5%, in particular at least about 50%.
  • a preferred composition has an elongation at break of about 1000%, more preferably of at most about 800%, more preferably of at most about 500%, in particular of at most about 250%, most preferably of at most about 100%.
  • the determination of the tensile strength and elongation at break can be determined with the aid of the so-called tensile test according to DIN EN ISO 527 and is known to the person skilled in the art.
  • composition according to the invention can be applied to its meterability in the cold or warm state in the laser sintering system, its layer application and powder bed state in the cold or warm state, their layer order in the laser sintering process, preferably in the current laser sintering process, in particular their coating on exposed surfaces and dimensional accuracy and mechanical properties of the specimens obtained are evaluated.
  • the composition comprises at least one additive which allows an adaptation of the mechanical, electrical, magnetic, flame-retardant and / or aesthetic powder or product properties.
  • the composition comprises at least one organic and / or inorganic additive such as glass, metal, for example aluminum and / or copper and / or iron, ceramic particles, metal oxides or pigments for varying the color, preferably titanium dioxide or soot.
  • the additive can also be made of a fiber, such as a carbon, glass and / or ceramic fiber, such. B. wollastonite.
  • a fiber such as a carbon, glass and / or ceramic fiber, such. B. wollastonite.
  • Fillers for adjusting the mechanical properties may also be selected from the group of metal oxides, or from calcium carbonate.
  • Flame-retardant additives can be selected, for example, from the group comprising metal hydroxides, such as Magnesium hydroxide or aluminum hydroxide, phosphorus compounds such. As red phosphorus or ammonium polyphosphate or brominated flame retardants
  • the composition comprises at least one additive which is used for the thermo-oxidative stabilization of the polymer and / or for UV stabilization.
  • It may be z. B. an antioxidant and / or a UV stabilizer.
  • an antioxidant can be obtained, for example, under the trade name Irganox or Irgafos from BASF (Ludwigshafen, Germany); a UV stabilizer can be obtained for example under the trade name Tinuvin on the company BASF.
  • an IR absorber is used as additive, which absorbs in the range of the wavelength used of the laser or the infrared heater.
  • This may be, for example, soot and / or copper hydroxide.
  • a functionalization could z.
  • Example consist in that the entire shaped body, one or more layers of the shaped body or even parts of one or more layers of the shaped body are electrically conductive equipped.
  • This functionalization can be achieved by conductive pigments, such. As metal powder, or by using conductive polymers such.
  • B. by the addition of polyaniline can be achieved. In this way, molded articles having printed conductors can be obtained, and these can be present both on the surface and within the molded article.
  • Polypropylene (PP) (polypropylene-polyethylene copolymer Borealis, Austria) with an MVR value of 30 cm 3/10 min was mixed with polyethylene glycol (PEG (molecular weight MW) 20000 D and 35000 D; Clariant, Switzerland) in a ratio of 30% by weight of PP
  • ZSE 27 MAXX Leistritz Extrusionstechnik GmbH, Nuremberg, Germany
  • the melt state zone temperature: from 220 to 360 ° C.
  • the ratio of polyethylene glycol was 20,000 and 35,000 50 wt% to 50 wt%.
  • PP-02 the ratio of polyethylene glycol was 20,000 and 35,000 80 wt% to 20 wt%.
  • the mixture was cooled to room temperature after extrusion on a conveyor belt with supply of room air and packaged.
  • the mixture was subsequently dissolved in water with stirring (1 kg of the mixture in 9 kg of water) and centrifuged (centrifuge TZ3, Carl Padberg Zentrifugenbau GmbH, Lahr, Germany).
  • the powder cake of the PP copolymer was washed twice with 10 liters of water in the centrifuge to remove the excess of polyethylene glycol.
  • the powder cake was then dried at 60 ° C. at 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Thereafter, the powder was sieved by means of a tumble sieve machine (mesh sieve: 245 ⁇ m, Siebtechnik GmbH, Mühlheim, Germany).
  • Table 1 Detailed description of the DSC method for the compositions according to the invention and the integration limit and AH m PBC of PEG / PEO for the determination of the PEG / PEO content in the sample.
  • Methods for calculating the content of additive in the composition according to the invention 1) Method 1: For PEG / PEO in polypropylene:
  • Table 1 presents the DSC method as well as the integration limits and enthalpy of fusion of a PEG sample ⁇ H mPEe ).
  • the content of polyethylene oxide (PEO) can also be determined when used as an additive in the preparation.
  • the PEG / PEO enthalpy of fusion is determined in the 2nd heating run (segment 6 of the DSC method). Based on these values and with the aid of formula 1, the PEG / PEO content in the sample is determined as follows 100
  • D Hp EG is the PEG enthalpy of fusion in the sample determined by the method as shown in Table 1.
  • & H mPEG is the PEG enthalpy of fusion of a pure PEG sample (171 J / g) determined with Polyglycol 20000 S (Technical grade, Clariant, Switzerland).
  • DH additive is the enthalpy of fusion of the additive in the sample determined by the DSC
  • ⁇ H mAdditive is the enthalpy of fusion of the pure additive determined by DSC method 3.
  • the crystallization and melting temperatures of the compositions were determined by DSC (DIN EN ISO 1 1357) on a DSC meter (Mettler Toledo DSC823). The evaluation took place with the help of the software STARe 15.0.
  • the changes in the crystallization and melting temperatures of the inventive compositions with additive ("PP 01", "PP 02") compared to a composition without the addition of an additive (“PP without additive”) are shown in Table 2 and FIG.
  • FIG. 1 shows DSC thermograms of the samples "PP without additive”, “PP 01” and “PP 02", which are usually plotted as a function of the temperature (° C.). Instead of the ordinate, a reference bar of 20 mW is given.
  • the respective melting peaks ie the temperature TM at which the composition melts, can be recognized for the samples "PP without additive", “PP 01” and “PP 02".
  • the lower curves show the crystallization temperatures TK of the samples "PP without additive", "PP 01” and "PP 02".
  • the comparative sample "PP without additive” shows a crystallization temperature of about 115 ° C. (see Table 2: sample “PP without additive”, column “TK 1. heating rate (HR)", Figure 1: solid line, top DSC thermogram).
  • PP 01 an additive content of 0.64% by weight in the dried composition according to the invention
  • MW molecular weight
  • a change in the melting temperature TM of the compositions according to the invention compared to a sample without additive can be observed in that for the sample without additive a "double" peak at about 132 ° C and 141 ° C is observed (see Table 2: “Sample without additive ", column” TM 2. HR “; FIG. 1: lowest solid line).
  • a melting peak is seen which shows a shoulder and a peak at about 137.5 ° C.
  • Table 2 Crystallization and melting temperatures of polypropylene copolymer Samples (PP) without additive ("PP without additive") and with addition of additive ("PP 01", "PP 02").
  • the additive consisted of a mixture of PEG with one
  • Example 2 The preparation of the composition according to the invention of Example 2 was carried out according to Example 1.
  • the polypropylene-polyethylene copolymer (type QR674K) used was obtained in Example 2 from Sabic Innovative Plastics (Bergen op Zoom, Netherlands); Polyethylene glycol (Clariant, Switzerland) with a molecular weight of 35,000 D was used as the additive.
  • the content of PEG was determined analogously to Example 1.
  • the melting temperature TM and crystallization temperature TK of the inventive composition "PP 03" in comparison to a sample “PP without additive” is shown in Table 3.
  • the comparative sample "PP without additive” shows a crystallization temperature of about 120 ° C (see Table 3: sample “PP without additive", column “TK 1. heating rate (HR)").
  • Table 3 Crystallization and melting temperature of the polypropylene copolymer samples (PP) without addition of additive ("PP without additive”) and with addition of additive ("PP 03").
  • the additive consisted of PEG with a molecular weight (MW) of 35,000 D.
  • PEKK Polyether ketone ketone
  • the powder cake was washed twice more with 150 ml of water in an Erlenmeyer flask and filtered off in each Buchner funnel to remove the excess of PEG or PEO.
  • the powder cake was then dried at 60 ° C. at 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Pulverpoben with the properties according to Table 5 were obtained.
  • the determination of the particle size distribution and sphericity (SPHT3) was carried out with Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) according to DIN ISO 13322-2. with the module X-Flow in a solution of Triton X in distilled water (3% by mass). Evaluation according to Xarea.
  • Table 4 Percent PEKK and PEG 20000 and PEG 35000 and PEO of the tested compositions.
  • the content of PEG or PEO in the dried compositions was determined by DSC (DIN EN ISO 1 1357) on a DSC meter (Mettler Toledo DSC823). The evaluation was carried out using the software STARe 15.0. The method or data for the evaluation are shown in Table 6. Since PEKK does not crystallize as a quasi-amorphous polymer at 10 ° C / min or 20 ° C / min, it was measured to initiate crystallization at a cooling rate of 2 ° C / min in Segment 5, deviating from the standard.
  • Table 6 Detailed description of the DSC method for the compositions according to the invention and the integration limit and AH ra PBC of PEG / PEO for the determination of the PEG / PEO content in the samples of PEKK.
  • the method for calculating the content of additive in the compositions according to the invention is carried out as described in Example 1.
  • the PEG / PEO enthalpy of fusion is determined in segment 8 instead of segment 6 of the DSC method.
  • PEKK-CF HT23, Advanced Laser Materials, Temple TX, USA
  • PEG polyethylene glycol
  • PEO polyethylene oxide
  • ZSE 27 MAXX Leistritz Extrusionstechnik GmbH, Nuremberg , Germany
  • the mixture after extrusion was cooled to room temperature on a conveyor belt at a cooling rate of 5 ° C / second (s) and packaged.
  • a portion of the mixture was subsequently dissolved in water at 70 ° C. with stirring (30 g in 150 ml of water), in a vibrating sieve machine (AS200, mesh size 300 ⁇ m, from Retsch, Haan, Germany). sieved and filtered off the filtrate ⁇ 300 pm by means of a Büchner funnel. Thereafter, the powder cake was washed twice with 150 ml of water in an Erlenmeyer flask and filtered off in each Buchner funnel to remove the excess of PEG or PEO. The powder cake was then dried at 60 ° C.
  • Table 8 Grain size distribution and DSC measurements of the tested (dried) compositions.
  • the content of PEG or PEO in the dried compositions was determined by DSC (DIN EN ISO 1 1357) on a DSC meter (Mettler Toledo DSC823). The evaluation was carried out using the software STARe 15.0. The method or data for Evaluation are shown in Table 9. The content of the PEG or PEO in the dried compositions is given in Table 8.
  • Table 9 Detailed description of the DSC method for the compositions according to the invention and the integration limit and AH ra PEG of PEG / PEO for
  • Example 1 Method for calculating the content of additive in the composition according to the invention was carried out as described in Example 1.
  • the PEG / PEO enthalpy of fusion is determined in segment 8 instead of segment 6 of the DSC method. From Table 8 it can be seen that the grain size can be adjusted as a function of the molar mass of PEG and PEO. With increasing molecular weight (PEO content), the crystallization point of the material can also be reduced. The process also shows another great advantage for filled PEKK-CF, similar to the unfilled PEKK.
  • PEKK-CF without additive which is extruded without PEG / PEO, is present as quasi amorphous granules, because the cooling is very fast after the extrusion (in the DSC shows a cold recrystallization with exothermic peak at about 255 ° C with subsequent endothermic melting peak at 306 ° C., TM 1.
  • HR A joint integration of the post-crystallization peak followed by the melting peak gives a melting enthalpy of 0 J / g and thus a crystallinity of 0%, XC 1 HR, in the granules).
  • amorphous materials tend to be unfavorable to laser sintering.
  • the PEKK-CF powder is partially crystalline with a melting point TM (1st HR) of about 284 ° C and a crystallinity XM (1st HR) of 14.4-19.2%.
  • TM (1st HR) melting point
  • XM crystallinity XM
  • Polyetherimide (PEI) (Ultem 1010, Sabic Innovative Plastics, Bergen op Zoom, The Netherlands) was blended with polyethylene glycol (PEG, molecular weight (MW) 35,000 D, Clariant, Switzerland) and polyethylene oxide (PEO: molecular weight (MW) 100,000 D; The Dow Chemical Company, Polyox WSR N10) in a ratio of 30% by weight PEI to 70% by weight PEG and / or PEO together in an extruder (ZSE 27 MAXX, Leistritz
  • the powder cake was washed twice with 1500 ml of water in an Erlenmeyer flask and filtered off in each Buchner funnel to remove the excess of PEG or PEO.
  • the powder cake was then dried at 60 ° C. at 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powders with properties according to Table 10 were obtained.
  • the determination of the particle size distribution and sphericity (SPHT3) was carried out with Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) according to DIN ISO 13322-2. with the module X-Flow in a solution of Triton X in distilled water (3% by mass). Evaluation according to Xarea.
  • Table 10 Percentage of PEI and PEG 20,000 and PEG 35,000 and PEO of the compositions tested, as well as data on the particle size distribution and DSC of the dried compositions.
  • the content of PEG or PEO in the dried compositions was determined by DSC (DIN EN ISO 1 1357) on a DSC meter (Mettler Toledo DSC823). The evaluation was carried out using the software STARe 15.0. The method or data for the evaluation are shown in Table 11. The content of the PEG or PEO in the dried compositions is given in Table 10.
  • Table 11 Detailed description of the DSC method for the compositions according to the invention and the integration limit and AH m PBC of PEG / PEO for the determination of the PEG / PEO content in the samples of PEI.
  • the method for calculating the content of additive in the composition according to the invention was carried out as described in Example 1 in segment 6 of the DSC method.
  • the grain size can be adjusted as a function of the molecular weight of PEG and PEO. Since PEI is melt-amorphous, no melting point and no crystallization point can be determined.
  • the mixture was cooled to room temperature after extrusion on a conveyor belt at a cooling rate of 4 ° C / second (s) and packed up.
  • a portion of the mixture was subsequently dissolved in water at 70 ° C. with stirring (30 g in 150 ml of water), in a vibrating sieve machine (AS200, mesh size 300 ⁇ m, from Retsch, Haan, Germany). sieved and filtered off the filtrate ⁇ 300 pm by means of a Büchner funnel. Thereafter, the powder cake was washed twice with 150 ml of water in an Erlenmeyer flask and filtered off in each Buchner funnel to remove the excess of PEG or PEO. The powder cake was then dried at 60 ° C.
  • Table 13 Grain size distribution and DSC measurements of the tested (dried) compositions.
  • the content of PEG or PEO in the dried compositions was determined by DSC (DIN EN ISO 1 1357) on a DSC meter (Mettler Toledo DSC823). The evaluation was carried out using the software STARe 15.0. The method or data for the evaluation are shown in Table 14. The content of the PEG or PEO in the dried compositions is given in Table 13.
  • Table 14 Detailed description of the DSC method for the compositions according to the invention and the integration limit and AH m PBC of PEG / PEO for determining the PEG / PEO content in the samples of polyphenylene sulfide.
  • Method for calculating the content of additive in the composition according to the invention is carried out as described in Example 1 in segment 6 of the DSC method.
  • the calculation of the crystallinity value by means of DSC is carried out with 1 12 J / g for theoretically 100% crystalline PPS.
  • the grain size can be adjusted as a function of the molar mass of PEG and PEO.
  • the particle size can be increased (see PPS-04 and PPS-05) if the proportion of the PEG having a molecular weight of 20,000 and 35,000 of 1: 1 is maintained ,
  • a polyamide 12 (PA12-16) (Grilamid L16 LM, EMS-Chemie, Switzerland) or a polyamide 12 (PA12-20) (Grilamid L20 LM, EMS-Chemie, Switzerland) were mixed with polyethylene glycol
  • Table 15 Percent PA12 and PEG 20000 and PEG 35000 and PEO of the tested compositions and MVR.
  • Table 16 Grain size distribution and DSC measurements of the tested (dried) compositions.
  • the content of PEG or PEO in the dried compositions was determined by DSC (DIN EN ISO 1 1357) on a DSC meter (Mettler Toledo DSC823). The evaluation was carried out using the software STARe 15.0. The method or data for the evaluation are shown in Table 17. The content of the PEG on the dried compositions is given in Table 16.
  • the calculation of the crystallinity value for polyamide 12 is carried out by means of DSC from the enthalpy of fusion or crystallization enthalpy with 209.5 J / g for theoretically 100% crystalline polyamide 12.
  • Table 17 Detailed description of the DSC method for the compositions according to the invention and the integration limit and AH m PBC of PEG / PEO for determining the PEG / PEO content in the sample of PA-12.
  • the method for calculating the content of additive in the composition according to the invention is carried out as described in Example 1.
  • the PEG / PEO enthalpy of fusion is determined in segment 6 of the DSC method.
  • the grain size can be adjusted depending on the melt viscosity of the polyamide 12 used. With a higher melt viscosity, which is equivalent to a higher molecular weight, a smaller particle size distribution is obtained when working with the same PEG content.

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Abstract

L'invention concerne une composition contenant au moins un polymère, le polymère se présentant sous la forme de particules polymères, et la composition contenant au moins un additif, l'additif représentant une proportion au maximum de 2% en poids de la composition. L'invention a également pour objet un procédé pour préparer la composition selon l'invention et un procédé pour fabriquer un composant comprenant la composition selon l'invention. Enfin, la présente invention porte sur l'utilisation de la composition selon l'invention.
EP18804556.1A 2017-11-14 2018-11-13 Composition pour procédé de fabrication additive Pending EP3710255A1 (fr)

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