EP3710255A1

EP3710255A1 - Composition for an additive manufacturing process

Info

Publication number: EP3710255A1
Application number: EP18804556.1A
Authority: EP
Inventors: Stoyan Frangov; Andreas Pfister
Original assignee: EOS GmbH
Current assignee: EOS GmbH
Priority date: 2017-11-14
Filing date: 2018-11-13
Publication date: 2020-09-23
Also published as: CN111836721A; WO2019096805A1; EP3710515A1; US20200308401A1; US20200362120A1; WO2019096806A1; CN111356719A

Abstract

The invention relates to a composition comprising at least one polymer, wherein the polymer is provided in the form of polymer particles, and the composition contains at least one additive, said additive having a proportion of maximally 2 wt.% of the composition. The invention additionally relates to a method for producing the composition according to the invention, to a method for producing a component comprising the composition according to the invention, and to the use of the composition according to the invention.

Description

Composition for additive manufacturing processes

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. In the manufacturing processes, 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.

For decades, processes in industrial development processes have been used to produce prototypes (rapid prototyping). However, the technological advances of the systems have also begun to produce parts that meet the quality requirements of a final product (rapid manufacturing).

In practice, the term "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.

As powdery materials for the production of moldings polymer systems are often used. Industrial users of such systems require good processability, high dimensional accuracy and good mechanical properties of moldings produced therefrom.

In the production of 3D components, the crystallization of the polymer begins during cooling. However, 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. In the case of insufficient layer adhesion due to premature crystallization, 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.

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.

Moreover, in order to adapt a material, for example a polymer system, in terms of its properties so that it is suitable for additive manufacturing processes, it is often necessary to add additives. Such 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. Also, 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.

Further undesirable effects with the addition of additives can also be expressed, for example, in a tendency to warp or a poor dimensional stability of the components, which severely limits the use of the additives or of systems with such additives in additive manufacturing processes. It is therefore an object of the present invention to provide a composition which is preferably suitable in additive manufacturing processes as a material for the production of moldings with a process-reliable mechanical stability and high dimensional accuracy. In particular, it is an object of the present invention to provide a composition having a larger process window.

This object is achieved by a 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

(a) at least one polymer,

wherein the polymer is in the form of polymer particles and wherein the polymer is selected from at least one thermoplastic polymer, and

(b) at least one additive,

wherein 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,

and or

wherein 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.

In its simplest embodiment, a composition according to the invention comprises a polymer or a polymer system which is selected from a thermoplastic polymer and an additive. In this context, 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. In particular, 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. Preferably, the additive is soluble in water at room temperature. In particular, an additive has a solubility of at least about 30 g / L of water.

Preferably, the composition according to the invention is in the form of a powder.

According to the invention, 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. Methods for determining the content of the additive in the composition or the polymer are known to the person skilled in the art and can be carried out, for example, by means of DSC (Differential Scanning Calorimetry, DIN EN ISO 1 1357). The additive is preferably bound to the polymer or the polymer particles, for example, on the surface or deposited.

According to the invention, 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. Under Crystallization temperature and melting temperature is to be understood as the peak temperature, as defined in DIN EN ISO 11357.

Methods for determining the crystallization temperature and the melting temperature are known to the person skilled in the art and can usually be measured by means of differential scanning calorimetry (DSC) according to DIN EN ISO 1 1357. In order to ensure comparability of the measurements of the polymer with and without additive, the determination by means of DSC is carried out in such a way that always the same methods are used while maintaining the same holding times, heating rates, initial temperature and final temperature.

The degree of crystallization can be measured by various analytical methods, such as DSC. Here, 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. However, 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. Surprisingly, it has now been found that 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.

Furthermore, the 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. In this case, 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. In particular, however, the composition of the invention is intended for use in laser sintering. The term "laser sintering" is synonymous with the term "selective laser sintering" to understand; the latter is just the older name. Furthermore, the present invention relates to a method for producing a composition according to the invention, the method comprising the following steps:

(i) providing at least one polymer, wherein the polymer is selected from at least one thermoplastic polymer,

(ii) mixing, preferably dispersing, the polymer with an additive,

(iii) removing, especially separating, the additive to obtain a composition,

wherein the 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,

and or

wherein the 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 .-%. By "providing" is meant both an on-site production and a delivery of a polymer or a polymer system.

In the following, the terms mixing, admixing, blending and compounding are understood to be synonymous. 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. Preferably, a mixing process takes place in the extruder, particularly preferably by melt extrusion. Alternatively, a mixing operation of the polymer with an additive, preferably in the melt, can take place in a kneader. However, 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. Insofar as the composition according to the invention is packaged, 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.

Finally, a 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. The term "solidifying" is understood to mean at least partial melting or melting with subsequent solidification or resolidification of the building material.

In this case, an advantageous method for producing a component has at least the following steps:

(i) applying a layer of a composition according to the invention and / or a composition prepared by a process according to the invention, preferably a powder, to a construction field,

(ii) selectively solidifying the coated layer of the composition at locations corresponding to a cross-section of the object to be produced, preferably by means of an irradiation unit, and

(Iii) lowering the carrier and repeating the steps of applying and solidifying until the component, in particular the three-dimensional object, is completed. In the present patent application, "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. As such 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. On the support, the building material is positioned so that its uppermost layer coincides with the plane which is to be solidified. In the course of the manufacturing process, in particular laser sintering, 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. Furthermore, 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. In this case, for example, 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.

With "rapid manufacturing" in particular processes for the production of components are meant, so the production of more than one same part, but in which the production z. B. by means of an injection molding tool is not economical or due to the geometry of the component is not possible, especially if the parts have a very complex design. Examples include parts for high-quality cars, racing or rally cars, which are produced only in small quantities, or spare parts for motor sports, where in addition to the small quantities and the timing of availability plays a role. Industries in which the parts of the invention are used, for. As the aerospace industry, the

Medical engineering, mechanical engineering, automotive engineering, the sports industry, household goods industry, electrical industry or lifestyle. Also of importance is the production of a variety of similar components, such as personalized components, such as prostheses, (inner ear) hearing aids and the like, whose geometry can be customized to the wearer.

Finally, 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. Further particularly advantageous embodiments and developments of the invention will become apparent from the dependent claims and the following description, wherein the claims of a particular category may also be developed according to the dependent claims of another category and features of different embodiments may be combined to form new embodiments.

As explained above, the composition according to the invention comprises at least one additive. Preferably, such an additive is immiscible with the at least one thermoplastic polymer. According to a preferred embodiment, 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.

According to a particularly preferred embodiment, the additive is selected from at least one polyol, in particular a partially crystalline polyol. Such 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. In particular, 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.

More preferably, the additive is selected from a surfactant such as at least one nonionic organic surfactant and / or polymeric surfactant. In particular, the surfactant is selected from sodium dodecyl sulfate. In particular, a preferred surfactant is present in partially crystalline form.

Insofar as 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.

According to a particularly preferred embodiment, 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. According to a further preferred embodiment, an advantageous

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. According to a preferred embodiment, 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. 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. In particular, 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.

The term "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. Finally, 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. Preferably, such a heteropolymer or copolymer and / or polymer blend is partially crystalline. By using one or more of the polymers mentioned (homopolymers, copolymers or polymer blends), it is possible to produce a pulverulent material which is at least partially semicrystalline. 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.

Insofar as the term "at least approximately" or "at most approximately" or "up to approximately" (etc.) is used in the present specification, this means that the said numerical value can have a possible deviation of 10 to 15%.

According to a particularly preferred embodiment, 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.

In principle, the at least one polypropylene can be present in atactic, syndiotactic and / or isotactic form. In 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. Most preferably, the polypropylene is selected from an isotactic polypropylene. Further, 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.

More preferably, 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.

Insofar as a 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

0.1 wt .-%, most preferably at least 0.2 wt .-%, and / or at most 2 wt .-%, preferably at most 1, 5 wt .-%, particularly preferably at most 1 Wt .-%, in particular at most 0.7 wt .-%, particularly preferably at most 0.5 wt .-%. Most preferably, the polypropylene is selected from a polypropylene-polyethylene copolymer.

Polyamides (PA) 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. The term "polyamides" is commonly used as a term for synthetic, technically usable thermoplastic polymers.

Inasmuch as 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 .-%. Preferably, 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.

According to a further preferred composition, the 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).

A further preferred embodiment comprises a polyether-ether-ketone-polyether-diphenyl-ether-ketone (PEEK-PEDEK) with the following repeating units:

Repeat unit A

and / or repeating unit B

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. At most, 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. Preferably, 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.

Inasmuch as 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:

Repeat unit A:

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

60 to 40 to 10 to 90, particularly preferably from about 60 to about 40. 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. Preferably, 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). According to a further preferred embodiment, 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. When using the above-mentioned composition, 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. According to a further preferred composition, the thermoplastic polymer is selected from at least one polyetherimide. In this case, the polyetherimide particularly preferably has repeating units according to the

Formula I

and / or repeat units according to the

Formula II

and / or repeat units according to the

Formula I

on. 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.

Preferably, 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

Formula IV

on. 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.

Preferably, 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 ^®.

According to a further preferred composition, the thermoplastic polymer is selected from polyarylene sulfide. Preferably, the polyarylene sulfide comprises a polyphenylene sulfide having recurring units according to

Formula V

on. 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® .

In particular, 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. Such 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.

Also, 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.

Finally, 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. According to a further preferred embodiment, 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 hydroxide or aluminum hydroxide). Further particularly preferred auxiliaries include polysiloxanes. Polysiloxanes can serve, for example, as flow aids for lowering the viscosity of the polymer melt and / or, in particular, for polymer blends as plasticizers.

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. For auxiliaries such as oxidation stabilizers, UV stabilizers, dyes, 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 .-%. For

Antiagglomerating agent and IR absorber, 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 .-%.

Polymer systems often have a positive and / or negative partial charge. In particular, if particles of the polymer system have different charges at different points of the surface, interactions, for example due to electrostatic, magnetic and / or Van der Waals forces between adjacent particles, can result, which result in undesired agglomeration of the polymer system particles , According to a further preferred embodiment, an advantageous embodiment comprises

Composition therefore at least one anti-agglomeration agent. The term "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.

The term "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.

According to a preferred embodiment, therefore, an advantageous composition comprises at least one anti-agglomeration agent. Such 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.

According to a further preferred embodiment, a first anti-agglomeration agent comprises silica. This can be produced by a wet-chemical precipitation process or by fumed silica. However, 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. In the following, silicon dioxide is also referred to as silica. According to a further preferred embodiment, 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.

According to a particularly preferred embodiment, the second anti-agglomeration agent is also a silicon dioxide, in particular pyrogenic silicon dioxide.

Of course, a composition according to the invention may also have more than two anti-agglomeration agents. In an advantageous composition, 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.

In principle, at least one or the two or more anti-agglomeration agents can be treated with one or more different hydrophobicizing agents. According to a further preferred embodiment, the anti-agglomeration agent has a hydrophobic surface. Such hydrophobing can be carried out, for example, with a substance based on organosilanes.

Furthermore, 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. By "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.

For the above-described additive manufacturing process powders are required with relatively round grain shape, since in the presence of angular particles during application of the powder layers can cause scars, which in particular an automatic construction process is difficult and the quality of the resulting components is deteriorated, especially their density and surface finish. Frequently, however, there is the problem of obtaining polymers or copolymers in the form of a powder with round particles.

The composition according to the invention can advantageously be used to obtain round particles. Preferably, such round particles are produced by means of melt dispersion, which advantageously have good flow properties.

In general, for 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.

The term 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.

To reduce the porosity of the resulting components, commonly used 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.

According to a further preferred embodiment, 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,

on.

Methods for determining the particle size or the particle size distribution are known to the person skilled in the art and can be carried out, for example, using a Camsizer XT measuring device (Retsch Technology, Germany) in accordance with DIN ISO 13322-2.

According to a preferred embodiment, 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 μm, 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).

It has also proved to be advantageous that 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. The particle surface determined by this method is also called the BET surface.

According to a preferred embodiment, 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. Particularly preferably, 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 process according to the invention for the preparation of the composition has already been explained in the introduction. According to another preferred method of preparation, 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. Particularly preferably, 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.

Preferably, a polypropylene granules 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. The melt volume

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).

According to a further preferred method of preparation, 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. Alternatively, a melt dispersion can take place in a kneader.

Following melt extrusion, 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). For example, in this case, 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. In the further course, 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.

In a next step, the addition of an additive to the composition according to the invention can be carried out. In particular, such an additive is selected from an anti-agglomeration agent. Preferably takes place an addition of the additive, in particular an antiagglomerating agent, in a mixer.

Finally, 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

Storage stability of the composition according to the invention is improved. Also, an advantageous packaging material prevents access of moisture, in particular humidity, to the composition according to the invention. As mentioned above, compositions according to the invention are for additive

Manufacturing processes, especially for laser sintering, suitable. Usually, 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. In addition, 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.

By "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.

It has also been shown that the tensile strength and elongation at break can be useful as material properties or as a measure of the processability of the composition according to the invention. According to a further preferred embodiment, 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%. At most, 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.

Furthermore, the 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.

Furthermore, it is advantageous if 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. In a preferred embodiment, 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.

Alternatively or additionally, the additive can also be made of a fiber, such as a carbon, glass and / or ceramic fiber, such. B. wollastonite. As a result, the absorption behavior of the powder can also be influenced. 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

Furthermore, it may be advantageous if 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. Such 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.

Furthermore, it may be advantageous if 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.

In addition to a functionalization by the addition of, for example, pigments, it is also possible in principle for compounds having particular functional properties to be present in one or more of the layers or in the entire molding. 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.

Further features of the invention will become apparent from the following description of exemplary embodiments in conjunction with the claims. It should be noted that the invention is not limited to the embodiments of the described

Embodiments, but is determined by the scope of the appended claims. In particular, the individual features in embodiments according to the invention can be realized in a different combination than in the examples given below. In the following explanation of some embodiments of the invention, reference is made to the accompanying figure. It shows: Figure 1 DSC thermograms of compositions of the invention ("PP 001", "PP002") compared to a composition containing no additive ("PP without additive"). Examples

example 1

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

Copolymer mixed to 70 wt .-% polyethylene glycol together in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremberg, Germany) in the melt state (zone temperature: from 220 to 360 ° C). For the sample "PP 01", the ratio of polyethylene glycol was 20,000 and 35,000 50 wt% to 50 wt%. For the sample "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. In order to dissolve the polyethylene glycol, 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 μm, Siebtechnik GmbH, Mühlheim, Germany). In a container mixer (Mixaco laboratory container mixer, 12 liters, Mixaco Maschinenbau Dr. Herfeld GmbH & Co. KG, Neuenrade, Germany), the powder was stirred for 1 min. With 0.1 wt .-% of an anti-agglomeration agent (Aerosil R974, Evonik Resource Efficiency, Hanau, Germany). Powders with the following grain size were obtained:

Sample "PP 01": d 50 = 45 pm

Sample "PP 02": d 50 = 40 pm The content of polyethylene glycol on the dried compositions ("PP 01", "PP 02") was determined by DSC (DIN EN ISO 11357) 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 1. The content of the polyethylene glycol on the dried compositions is named in Table 2 (below). In the same way, the content of polyethylene oxide (PEO) can be determined when it is used as an additive in the production.

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.

n.b. = not determined

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 ). In the same way, 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

formula 1

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).

2) Method 2: For PEG / PEO in Partially Crystalline and Amorphous Polymers and Polymer Blends:

Analogous to the determination of the content of PEG / PEO in polypropylene (see method 1). Notwithstanding Method 1, instead of 220 ° C for the starting temperature (segments 3 + 4) and final temperature (segments 2 + 3 + 6) in the DSC, the temperature used for the semicrystalline polymer according to DIN EN ISO 1 1357 is used. However, the maximum end temperature is limited to 360 ° C to avoid thermal degradation of the PEG / PEO.

3) Method 3: For semi-crystalline additives by DSC:

Analogous to the determination of the content of PEG / PEO in semicrystalline polymers (see Method 2). By way of derogation, the temperature used for the semicrystalline polymer or the additive according to DIN EN ISO 1 1357 is used for the starting temperature (segments 3 + 4) and final temperature (segments 2 + 3 + 6) in the DSC. Depending on which temperature is higher, this is used. The determination of the additive content is analogous to the determination of the PEG / PEO content. By contrast, however, DSC method 3 is used.

Formula 2

DH _additive is the enthalpy of fusion of the additive in the sample determined by the DSC

Method 3.

^ 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. In the upper three curves, 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".

Upon addition of additive, both a change in the crystallization temperature TK and the melting temperature TM can be observed. 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). With an additive content of 0.64% by weight in the dried composition according to the invention ("PP 01"), in this case of PEG having a molecular weight (MW) of 35 000 D and 20 000 D in the ratio 50: 50, a reduction of the crystallization temperature by about 8 ° C., namely from about 1 15 ° C. to about 107 ° C. (see Table 2: sample "PP 01", column "TK 1 HR", Figure 1: dotted line, second top DSC thermogram). At a content of PEG of 1, 09 wt .-% in the dried composition according to the invention ("PP 02") (ratio PEG MW 35 000 D to MW 20 000 D: 20: 80) results in a lowering of the crystallization temperature of about 15 C., from about 15.degree. C. to about 100.degree. C. (see Table 2: sample "PP 02", column "TK 1. HR"; Figure 1: dashed line, third uppermost DSC thermogram).

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). By contrast, when the content of the additive is 0.64% by weight, a melting peak is seen which shows a shoulder and a peak at about 137.5 ° C. (see Table 2: Sample "PP 01", column "TM 2 HR "; Figure 1: lowest dotted line); for the sample "PP 02", which has a content of additive of 1, 09 wt .-%, finally results in a peak at about 135 ° C (see Table 2: sample "PP 02", column "TM 2. HR Figure 1: lowest dashed line).

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

Molecular weight (MW) of 35,000 D and 20,000 D in the ratio as shown.

n / A. = not applicable TM = melting temperature

TK = crystallization temperature HR = heating rate

XC = crystallinity dH = enthalpy of fusion

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. A powder with the following particle size was obtained: PP-03: d50 = 29 μm

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. When additive is added, it is again possible to observe a change in the crystallization temperature TK and in the melting temperature TM in comparison with the sample without additive. 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)"). With a content of additive of 0.08 wt .-% in the dried composition according to the invention ("PP 03"), in the present case of PEG having a molecular weight (MW) of 35 000 D, results in a lowering of the crystallization temperature by about 12 ° C, namely from about 120 ° C to about 108 ° C (see Table 3: sample "PP 03", column "TK 1. 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.

Example 3:

Polyether ketone ketone (PEKK) (Kepstan 6004, Arkema, France) was used with

Polyethylene glycol (PEG, molecular weight (MW) 20,000 D and 35,000 D; Clariant,

Switzerland) or polyethylene oxide (PEO: molecular weight (MW) 100 000 D, The Dow Chemical Company, Polyox WSR N10) in a ratio of 30-40 wt .-% PEKK to 60-70 wt .-% PEG and / or PEO together in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremberg, Germany) in the melt state

(Zone temperature: 340 ° C). The exact conditions are listed in Table 4. The mixture was extruded on a conveyor belt with a Cooling rate of 5 ° C / second (s) cooled to room temperature and packaged. In order to dissolve the PEG or PEO, 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 μm, from Retsch, Haan, Germany). sieved and filtered off the filtrate <300 pm by means of a Büchner funnel. 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.

na = not applicable Table 5: 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 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. By way of derogation, the PEG / PEO enthalpy of fusion is determined in segment 8 instead of segment 6 of the DSC method.

From Table 5 it can be seen that the grain size can be adjusted depending on the molecular weight 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 big advantage for PEKK. Unfilled PEKK (60:40 T / I copolymer) (PEKK without additive), which is extruded without PEG / PEO, is present as quasi-amorphous granules, because the cooling takes place very rapidly after the extrusion (typically> 100 ° C./s) , In the DSC, a cold recrystallization with exothermic peak at about 256 ° C with subsequent endothermic melting peak at 306 ° C, TM 1. HR. A joint integration of Nachkristallisationspeak followed by melting peak results in a melting enthalpy of 0 J / g and thus a crystallinity of 0%, XC 1. HR, in the granules. However, amorphous materials tend to be unfavorable to laser sintering. By means of melt emulsification is achieved that the PEKK powder partially crystalline with a melting point TM (1st HR) of about 284 ° C and a crystallinity XM (1st HR) of 14.4-19.2%. The crystallinity value was calculated by DSC at 130 J / g for theoretically 100% crystalline PEKK (source Cytec, Technichal data Sheet, PEKK Thermoplastic Polymer, Table 3). Sphericities of> 0.9 (Camsizer XT, SPHT3) were obtained for all powders except PEKK-03.

Example 4:

A carbon fiber filled PEKK (PEKK-CF, HT23, Advanced Laser Materials, Temple TX, USA) was blended with polyethylene glycol (PEG, molecular weight (MW) 20,000 D and 35,000 D, Clariant, Switzerland) and polyethylene oxide (PEO: molecular weight (MW 100,000 D; The Dow Chemical Company, Polyox WSR N 10) in a ratio of 30% by weight of PEKK to 70% by weight of PEG and / or PEO together in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremberg , Germany) in the melt state (zone temperature: 340 ° C). The exact conditions are listed in Table 7. The mixture after extrusion was cooled to room temperature on a conveyor belt at a cooling rate of 5 ° C / second (s) and packaged. In order to dissolve the PEG or PEO, 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 μm, 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. at 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powders having the properties shown in Table 8 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 7: Percentage of PEKK-CF and PEG 20,000 and PEG 35,000 and PEO, respectively, of the compositions tested.

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

Determination of PEG / PEO content in samples of carbon fiber filled PEKK (PEKK-CF).

Method for calculating the content of additive in the composition according to the invention was carried out as described in Example 1. By way of derogation, 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. Also 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). However, amorphous materials tend to be unfavorable to laser sintering. By melt emulsification is achieved that 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%. Calculation of the crystallinity value by DSC is carried out at 130 J / g for theoretically 100% crystalline PEKK (source Cytec, Technichal data Sheet, PEKK Thermoplastic Polymer, Table 3), taking into account the carbon fiber content of 23%.

Example 5:

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

Extrusionstechnik GmbH, Nuremberg, Germany) in the melt state (zone temperature: 340 ° C). The exact conditions are listed in Table 9. The mixture after extrusion was cooled to room temperature on a conveyor belt at a cooling rate of 5 ° C / second (s) and packaged. In order to dissolve the PEG or PEO, a portion of the mixture was subsequently dissolved in water at 70 ° C. with stirring (10 g in 1500 ml of water), in a vibrating sieve machine (AS200, mesh size 300 μm, from Retsch, Haan, Germany). sieved and filtered off the filtrate <300 pm by means of a Büchner funnel. 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.

From Table 10 it can be seen that 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.

Example 6

Linear polyphenylene sulfide (PPS) (MVR (315 ° C, 2.16 kg) = 33 cm ^3/10 min) was mixed with polyethylene glycol (PEG (molecular weight MW) 20000 D and / or 35000 D; Clariant, Switzerland) or Polyethylene oxide (PEO: molecular weight (MW) 100,000 D; The Dow Chemical Company, Polyox WSR N10) in a ratio of 30-40% by weight PPS to 60-70% by weight PEG and / or PEO together in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremberg, Germany) in the melt state mixed (zone temperature: 290 ° C). The exact conditions are listed in Table 12. 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. In order to dissolve the PEG or PEO, 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 μm, 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. at 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powders having the properties shown in Table 13 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 12: Percent PPS and PEG 20,000 and PEG 35,000 and PEO, respectively, of the compositions tested.

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.

From Table 13 it can be seen that the grain size can be adjusted as a function of the molar mass of PEG and PEO. By increasing the PPS content from 30% to 40% by weight, 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 ,

Example 7:

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

(PEG, molecular weight (MW) 20,000 D Clariant, Switzerland) in a ratio of 45% by weight PA12-16 to 55% by weight PEG together in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremberg, Germany) mixed in the melt state (zone temperature: 260 ° C). The exact conditions are listed in Table 15. The mixture was extruded on a conveyor belt with a Cooling rate of 4 ° C / second (s) cooled to room temperature and packaged. In order to dissolve the PEG or PEO, 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 μm, from Retsch, Haan, Germany). sieved and filtered off the filtrate <300 pm by means of a Büchner funnel. 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. 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 having the properties shown in Table 16 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 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.

From Table 16 it can be seen that 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.

Claims

claims

1. Composition comprising

(a) at least one polymer,

wherein the polymer is preferably in the form of polymer particles and wherein the polymer is selected from at least one thermoplastic polymer, and

(b) at least one additive,

wherein the at least one additive has a proportion of the composition 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 wt .-%, most preferably of at least 0.2 wt .-%,

and or

wherein the additive has a proportion of the composition 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 wt .-%, having.

2. The composition of claim 1, wherein the additive is selected from at least one semi-crystalline polymer, a partially crystalline polyol, a semi-crystalline

Surfactant and / or a partially crystalline protective colloid.

3. Composition according to claim 1 or 2, wherein the additive is selected from at least one polyol, preferably from at least one polyethylene glycol and / or from at least one polyethylene oxide and / or from at least one polyvinyl alcohol and / or from poloxamer and / or from sodium dodecyl sulfate, wherein the polyol is more preferably selected from at least one polyethylene glycol.

4. A composition according to any one of the preceding claims, wherein the

Crystallization temperature of the composition by at least 2 ° C, preferably by at least 3 ° C, more preferably by at least 4 ° C, in particular by at least 5 ° C, compared to the thermoplastic polymer without additive and / or wherein the difference DTK / TM of Crystallization temperature (TK) and the melting temperature (TM) by at least 1 ° C, preferably by at least 3 ° C, more preferably increased by at least 5 ° C.

5. A composition according to any one of the preceding claims, wherein the thermoplastic polymer is selected from at least one polyetherimide, polycarbonate, polysulfone, polyphenylene sulfone, polyphenylene oxide, polyethersulfone, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylate copolymer,

Polyvinyl chloride, polyacrylate, polyester, polyamide, polypropylene, polyethylene, polyaryletherketone, polyether, polyurethane, polyimide, polyamideimide, polyolefin, polyarylene sulfide, in particular of at least one polyamide and / or polypropylene, and copolymers thereof and / or at least one polymer blend based on the abovementioned Polymers and / or copolymers.

6. The composition according to claim 5, wherein 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 1 12, polyamide 1212, polyamides PA6T / 6I, Poly-m-xylylene adipamide (PA MXD6), polyamides 6 / 6T, polyamides PA6T / 66, PA4T / 46 and platamid M1757, copolymers thereof and / or wherein the at least one polypropylene is selected from isotactic polypropylene and / or its copolymers with polyethylene or with maleic anhydride.

7. A composition according to any one of the preceding claims, wherein the

polymer

at least one partially crystalline polymer, preferably a partially crystalline copolymer and / or a partially crystalline polymer blend.

8. The composition according to claim 7, wherein the polymer and / or the copolymer and / or the polymer blend has a melting temperature of at least about 50 ° C, preferably of at least about 100 ° C, and / or wherein the polymer and / or the copolymer and / or the polymer blend has a melting temperature of at most about 400 ° C, preferably of at most about 350 ° C, having.

9. The composition according to any one of claims 5 to 8, wherein the

Polyaryletherketone is selected from the group of polyether ketone ketone (PEKK) and / or from the group of polyetheretherketone-polyetherdiphenyletherketone (PEEK-PEDEK).

10. The composition according to any one of claims 5 to 9, wherein the polyether ketone ketone following repeating units

Repeat unit A:

n2, wherein the ratio of the repeat unit A to repeat unit

B is preferably about 60 to about 40.

1 1. A composition according to any one of claims 5 to 10, wherein the polyaryletherketone a melting temperature of up to 330 ° C, preferably up to 320 ° C, in particular up to 310 ° C, and / or wherein the polyaryletherketone a glass transition temperature of at least 120 ° C, preferably of at least 140 ° C, in particular of at least 160 ° C., having.

12. The composition according to any one of claims 7 to 1 1, wherein the polymer blend is a polyaryletherketone polyetherimide, a polyaryletherketone polyetherimide

Polycarbonate, a polyphenylene sulfide polyetherimide and / or a polyetherimide polycarbonate.

A composition according to any one of the preceding claims, wherein the composition further comprises an adjuvant.

14. A composition according to any one of the preceding claims, wherein the composition comprises at least one anti-agglomeration agent,

wherein the proportion of the at least one antiagglomerating agent in the composition is at least 0.01% by weight, preferably at least 0.02% by weight,

and or

wherein the proportion of the at least one anti-agglomeration agent in the composition at not more than 1 wt .-%, preferably at most 0.5 wt .-%, more preferably at most 0.2 wt .-%, in particular at most 0.1 wt. %, lies.

A composition according to any one of the preceding claims, wherein the composition has a bulk density of at least about 350 kg / m ³ and / or at most about 650 kg / m ³ .

16. A process for preparing a composition, the process comprising the steps of:

(ii) mixing, preferably dispersing, the polymer with an additive,

(iii) removing the additive to obtain a composition,

wherein the 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,

and or

wherein 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 wt .-%.

17. A method for producing a component, in particular a three-dimensional

Object comprising the steps:

(i) applying a layer of a composition according to one of claims 1 to 15 and / or a composition prepared by a process according to claim 16, preferably a powder, to a construction field,

(Iii) lowering the carrier and repeating the steps of applying and solidifying until the component, in particular the three-dimensional object, is completed.

18. A composition according to any one of claims 1 to 15, wherein the composition is preferably obtainable by a method according to claim 17.

19. A component, in particular a three-dimensional object, comprising a composition according to one of claims 1 to 15, wherein the component is preferably obtainable by a method according to claim 17.

20. Use of a composition according to one of claims 1 to 15, which has been produced in particular by a process according to claim 16, for 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, especially for use in laser sintering.