Methods for programming polymer molded parts made from polymers with shape memory properties or with thermoresponsive properties

Abstract

A method for programming a polymer molded part made of a second shape-memory polymer is proposed, in which the polymer molded part is transferred from a first mold to a second mold by applying mechanical deformation forces, such that it can be switched back to the first mold when heated to the switching temperature of its second shape-memory polymer. The invention provides that a programming tool made of a first shape-memory polymer is used for programming, which is programmed such that it can be switched from a first mold to a second mold when its first shape-memory polymer is heated to its switching temperature.During programming, the polymer molded part is inserted into the mold space of the programming tool. The latter then switches from its first mold to its second mold to transfer this mold change to the polymer molded part and program it from its first mold to its second. The programmed polymer molded part is then removed from the mold space of the programming tool. Furthermore, it is possible to combine the polymer molded part with other molded parts during its programming, for example, to create hybrid components.

Description

[0001] The invention relates to a method for programming at least one polymer molded part made of at least one second polymer with shape memory properties and / or with thermoresponsive properties, in that the polymer molded part is transferred from a first mold to a second mold by applying mechanical deformation forces, so that it can be switched back into the first mold when heated to the switching temperature of its at least one second polymer with shape memory properties and / or with thermoresponsive properties.

[0002] Shape memory polymers, also known as shape memory polymers, are polymers typically composed of at least two polymer components or a single polymer component with various segments. These segments include hard segments, which also function as lattice points, and soft segments, which connect the lattice points and are also referred to as switching segments.

[0003] The soft or switching segments are elastic at elevated temperatures (in which case they exist primarily in an amorphous form), while they are rigid at lower temperatures (in which case they exist primarily in a crystalline or semi-crystalline form). Such shape-memory polymers can be programmed with respect to their shape by heating them to a temperature that corresponds at least to the so-called switching temperature, at which the phase transition or melting transition of the soft or switching segments occurs. At such a temperature, the shape-memory polymer is then deformed, after which it is cooled, while maintaining the deformation force, to its so-called shape-fixing temperature. This temperature corresponds to the crystallization temperature of the soft or switching segments and can be in the range of the switching temperature, but is usually lower. The soft orSwitching segments then exist again in a predominantly crystalline or semi-crystalline form, so that the shape is retained. However, this shape is only temporary insofar as when such a mechanically deformed shape memory polymer, "programmed" in this way, is heated to a specific temperature, namely its switching temperature, the soft segments (switching segments) are converted back into their predominantly amorphous form, so that they can no longer counteract the restoring force induced by the hard component (lattice points) and the shape memory polymer returns to its original shape; the mechanical deformation is thus "reversed". Furthermore, some shape memory polymers can also be programmed by cold forming, by heating the polymers at a temperature below their switching temperature, e.g.At ambient temperature, they are deformed and, if the mold fixing temperature is lower, cooled to their mold fixing temperature. Even in this case, the deformation is only temporary, as re-deformation occurs upon reheating, at least to the switching temperature, to transition the soft segments (switching segments) into the amorphous phase and thereby relax the mechanical stresses induced by cold forming.

[0004] In addition to shape memory, thermoresponsive polymers can also exhibit temperature memory. This means that when the shape memory effect is triggered, the material returns to its original shape at approximately the temperature at which the mechanical deformation was initially introduced. Polymers with semi-crystalline network structures, such as thermoplastic polyurethane elastomers, exhibit this type of material behavior (N. Fritzsche, T. Pretsch in Macromolecules 47, 2014, 5952-5959; N. Mirtschin, T. Pretsch in RSC Advances 5, 2015, 46307-46315).

[0005] A polymer with shape memory and thermoresponsive properties is known, for example, in the form of a thermoplastic polyester urethane from DE 10 2018 007 028 A1. In this case, it contains, on the one hand, hard segments containing polyurethane units obtained by polyaddition of the isocyanate groups of a diisocyanate with the hydroxyl groups of a diol serving as a chain extender, forming urethane groups. On the other hand, the known thermoplastic polyester polyurethane contains crystallizable soft segments containing polyester units that are linked to the hard segments by polyaddition of corresponding polyester diols or polyols with the isocyanate groups of the diisocyanate, forming urethane groups.The polyester diols or polyols were obtained by polycondensation of the hydroxy groups of another diol with a dicarboxylic acid or with its derivatives to form ester groups, wherein the polyester diols or polyols of the polyester units of the soft segments have an average molar mass between 1500 g / mol and 10000 g / mol.

[0006] Applications for such polymers with shape memory properties, and especially with thermoresponsive properties, include various medical applications such as bandages, compresses, insoles, and the like, as well as everyday objects like dishes, toys, pacifiers, textiles, mattresses, hoses, spindles, and the like. Another interesting application lies in information carriers, for example, for the tamper-proof marking of goods to verify their authenticity. This involves, for instance, utilizing the fact that a code applied to the goods—for example, a machine-readable and / or otherwise optically uniquely identifiable code—only becomes visible or readable (or only until) the information carrier made from such polymers is heated to its switching temperature, after it has been (temporarily) deformed using the programming described above.After processing, such polymer molded parts possess shape and temperature memory. In addition to thermoresponsiveness, thermochromic properties can also be provided, for example, if the polymer molded part has been printed or treated with appropriate thermochromic dyes or pigments. Other well-known applications include, for example, technical components such as gears (see, e.g., EP 3 564 023 A1), jewelry (see, e.g., DE 10 2019 002 261 A1), insulating materials made of foamed shape-memory polymers (see, e.g., DE 10 2019 002 261 A1), actuators (see, e.g., DE 10 2020 001 380 A1), and the like.

[0007] Furthermore, polymers with shape memory properties and / or thermoresponsive properties are known which exhibit bidirectional shape memory and can therefore be thermoreversibly switched. The switching segments of such bidirectional shape memory polymers undergo a shape change during the transition between their predominantly crystalline state and their predominantly amorphous state. This change occurs when the polymer is cooled below its crystallization temperature or heated to its switching temperature range, allowing it to be reversibly switched back and forth between two bistable shape states. In other words, the appropriately programmed polymer deforms itself back and forth under specific temperature conditions. Such polymers are known, for example, from T. Pretsch, M. Bothe: “Bidirectional actuation of a thermoplastic polyurethane elastomer”, Journal of Materials Chemistry A, 20 (2013), 14491-14497.The reciprocating deformation of such two-way shape memory polymers can occur more or less purely through temperature induced processes, without the need for applied deformation forces. Furthermore, two-way shape memory polymers are known which exhibit their two-way shape memory properties particularly under the influence of a permanent mechanical preload, such as from permanent pressure, so that they are under permanent stress to promote the crystallization of the soft segments during cooling, as described, for example, in the article by M. Bothe, T. Pretsch: “Two-way shape changes of a shape memory poly(ester urethane)” in Macromol. Chem. Phys. 213 (2012), 213, 2378-2385.

[0008] Thermoplastic polyurethanes with shape memory properties and / or thermoresponsive properties – whether they are primarily compact or formed in the form of foams – are therefore versatile materials with convincing properties, whereby their polymer units forming the soft segments are usually made up of semi-crystalline molecular chains, so that it is possible to program a thermoreversible shape memory effect, including optionally a two-way shape memory effect, into them after processing by means of a thermomechanical treatment, the so-called programming (see above).

[0009] Programming polymer molded parts made from polymers with shape memory properties and / or thermoresponsive properties is generally quite complex, as the polymer molded part is transferred from a first mold to a second mold by applying mechanical deformation forces (see above), from which the polymer molded part can be switched back to its first mold when it is heated to the switching temperature of its polymer with shape memory properties and / or thermoresponsive properties.This applies both to so-called one-way shape memory polymers with a permanent first form and a programmed temporary second form (the one-way shape memory polymer must then be programmed again into the same or a different second form to trigger the shape memory effect) and to so-called two-way shape memory polymers, which can be reversibly switched back and forth between their first form and their programmed second form by heating them to the range of their switching temperature or cooling them to the range of their crystallization temperature.The programming of the polymer molded part is usually carried out using a tensile testing machine for the controlled local application of the required deformation forces in a thermal chamber, in order to heat the polymer with shape memory properties and / or with thermoresponsive properties to its switching temperature range while maintaining the mechanical deformation forces and then to cool it to its crystallization temperature range.

[0010] The article “Highly Shrinkable Objects as Obtained from 4D Printing” by D. Chalissery et al., Macromol. Mater. Eng., 307, 2100619 (2022) describes a method for in-situ programming of shape memory polymers during 3D printing. This is achieved by minimizing the temperature difference between the 3D printer nozzle temperature and the glass transition temperature of the shape memory polymer's soft segments. This prevents the hard segments of the shape memory polymer from completely melting and remaining under mechanical stress after printing. In this way, the printed polymer part can be transformed from its initial shape, acquired during printing, into a second shape with a shrinkage adjustable via the printing parameters, once it is reheated to a temperature at least equal to the melting temperature of its soft segments.

[0011] US Patent 2004 / 0199242 A1 describes various methods for manufacturing medical stents. In a first embodiment, a mandrel is provided which is coated with a biocompatible polymer. A plurality of expandable rings made of biocompatible metals are then applied to the biopolymer coating of the mandrel. The assembly, consisting of the mandrel, the biocompatible coating, and the rings, is then provided with an external polymeric coating by immersing it in a polymer solution. The coating polymer is selected according to the elasticity of the metal alloy of the rings, and a variety of polymers with different elasticities, including shape-memory polymers, can be used. After the coating applied by immersion coating has cured, the finished stent is removed from the mandrel.According to an alternative embodiment, an inner tube made of thermoplastic polymers is arranged on a mandrel, after which a plurality of expandable rings made of biocompatible metals are applied to the inner tube. An outer tube made of thermoplastic polymers is then arranged on the inner tube with the rings. Finally, the assembly supported by the mandrel, consisting of the inner tube, the outer tube, and the rings inserted between them, is fused together by being placed in a shrink tube, the latter of which is heated, in particular by means of lasers. The finished stent is then removed from the mandrel and the shrink tube.

[0012] The invention is based on the objective of proposing a novel method for programming polymer molded parts made of at least one second polymer with shape memory properties and / or with thermoresponsive properties of the type mentioned above, which makes it possible to program the polymer molded part from its first shape section by section or completely into practically any second shape while ensuring relatively simple and fast programming of the polymer molded part.

[0013] According to the invention, this problem is solved in a method of the type mentioned at the outset by the fact that the programming of the polymer molded part comprises the following steps: (a) providing a - having a form space or - insertable into a mold space of a molding tool Programming tool made of at least one first polymer with shape memory properties and / or with thermoresponsive properties, which is programmed such that when the at least one first polymer with shape memory properties and / or with thermoresponsive properties is heated to its switching temperature, it can be switched from a first shape to a second shape; (b) - Introducing the polymer molded part made of at least one second polymer with shape memory properties and / or with thermoresponsive properties into the mold space of the programming tool, or - Inserting the programming tool into the mold space of the mold tool and introducing the polymer molded part made of at least one second polymer with shape memory properties and / or with thermoresponsive properties into the mold space of the mold tool; (c) Heating the programming tool at least to the switching temperature of its at least one first polymer having shape memory properties and / or thermoresponsive properties, transferring it from its first mold to the second mold in order to program the polymer molded part made from the at least one second polymer having shape memory properties and / or thermoresponsive properties from its first mold to its second mold; and (d) Removing the polymer molded part programmed into the second mold from the at least one second polymer having shape memory properties and / or thermoresponsive properties - from the form space of the programming tool or - from the mold space of the molding tool.

[0014] The invention therefore provides that the programming of the polymer molded part from at least one second polymer with shape memory properties and / or with thermoresponsive properties, during which mechanical deformation forces act on the polymer molded part to transfer it from its first shape to its second shape, is carried out by means of a programming tool which in turn is formed from at least one - in particular different or even the same - first polymer with shape memory properties and / or with thermoresponsive properties, by the latter being heated at least to its switching temperature during the above process step (c), so that the programming tool is transferred from its first shape to its second shape.The deformation of the programming tool is transferred to the polymer molded part in contact with it as a result of a corresponding deformation force being applied, so that the latter can be programmed from its first shape to its second shape with a complementary shape change. In this way, a controlled plastic deformation of the polymer molded part from the second polymer with shape memory properties and / or thermoresponsive properties is ensured during its programming, triggered by heating the programming tool to the switching temperature of its first polymer with shape memory properties and / or thermoresponsive properties. Complex, essentially complete or only local deformations of the polymer molded part are also possible during its programming through corresponding complementary programming of the programming tool.

[0015] The programming tool can itself be designed essentially like a mold and have at least one mold space, which in particular has an inner contour that is essentially complementary to the outer contour of the polymer molded part, wherein the polymer molded part is inserted into the mold space of the programming tool during the above process step (b). Alternatively, it is also conceivable that the programming tool is designed like a mold insert and is inserted into the mold space of, for example, a conventional mold during process step (b), after which the polymer molded part is inserted into the mold space of the mold provided with the programming tool.In this case as well, the inner contour of the mold space of the mold tool equipped with the programming tool is chosen to be essentially complementary to the outer contour of the polymer mold part in order to transfer the deformation forces of the programming tool induced during the programming of the polymer mold part according to step (c) to the polymer mold part in contact with it.

[0016] The polymer molded part is then cooled, in particular to at least the mold fixing temperature of its at least one second polymer with shape memory properties and / or thermoresponsive properties, and removed from the mold chamber of the programming tool or the mold chamber of the mold equipped with it. The polymer molded part is now programmed into its second shape and is able to return to the first shape as soon as it is heated to its switching temperature.

[0017] In an advantageous embodiment, it can be provided that the at least one switching temperature of the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is selected to be greater than or equal to the at least one switching temperature of the second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part to be programmed, so that when the programming tool is heated to the switching temperature of its at least one first polymer with shape memory properties and / or with thermoresponsive properties according to step (c), the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part is also heated at least to its switching temperature in order to plastically deform it from its first shape to its second shape during its programming.whereupon at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part is cooled at least to its shape fixing temperature.

[0018] If cold programming is desired depending on the material of the polymer molded part (see above), it is also conceivable that the at least one switching temperature of the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is chosen to be lower than the at least one switching temperature of the second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part to be programmed, so that when the programming tool is heated to the switching temperature of its at least one first polymer with shape memory properties and / or with thermoresponsive properties according to step (c), the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part is cold-formed in order to program it from its first shape to its second shape.where at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part is cooled, in particular, at least to its mold fixing temperature.

[0019] In a further advantageous embodiment, it can be provided that at least one first polymer with shape memory properties and / or thermoresponsive properties of the programming tool is selected from the group of thermoplastic polymers, in particular from the group of polyether urethanes and polyester urethanes. The programming tool can thus be produced using any known thermoplastic processing methods, such as...The polymer can be manufactured by extrusion, injection molding, hot pressing or the like, whereby, in the case of the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool, it is a disposable shape memory polymer, and can be reused after its use for programming the polymer molded part, for example by reprogramming it by means of a thermomechanical treatment or by melting it down and using it to produce another programming tool.On the other hand, it is of course also conceivable that the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is selected from the group of two-way shape memory polymers, so that after the programming of the polymer molded part, during which it has been transferred from its first shape to its second shape by heating at least to its switching temperature, it is cooled again at least to its shape fixing temperature in order to switch it back from its second shape to its first shape in order to be able to program a new polymer molded part.

[0020] Examples of thermoplastic polymers found to be suitable for the programming tool, possessing shape memory and / or thermoresponsive properties, include linear block copolymers, preferably polyurethanes and polyurethanes with ionic or mesogenic components, block copolymers of polyethylene terephthalate and polyethylene oxide, block copolymers of polystyrene and poly(1,4-butadiene), ABA triblock copolymers of poly(2-methyl-2-oxazoline) (A-block) and polytetrahydrofuran (B-block), multiblock copolymers of polyurethanes with poly(ε-caprolactone) switching segments, block copolymers of polyethylene terephthalate and polyethylene oxide, and block copolymers of polystyrene and poly(1,4-butadiene). Furthermore, thermoplastic polyurethane elastomers have proven suitable whose hard-segment-forming phase consists of a diisocyanate, such as...The compound consists of methylenediphenyl diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HMDI), toluene-2,4-diisocyanate (TDI), or 1,5-pentane diisocyanate (PDI), and a diol such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, or 1,10-decanediol. Both the aforementioned diisocyanates and the polyols can be used individually or in any mixture with each other. The soft segment in such thermoplastic polyurethane elastomers can be, for example, an oligoether, in particular polyethylene oxide, polypropylene oxide, polytetramethylene ether glycol (PTMEG), or a combination of 2,2-bis(4-hydroxyphenyl)propane and propylene oxide. Likewise, the soft segment can be, for example,The oligoester may be an oligoester, in particular polyethylene adipate, polypropylene adipate, polybutylene adipate, polypentylene adipate, or polyhexalene adipate, although other oligoesters have also proven useful. The oligoesters can be prepared, for example, by reacting ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, or 1,10-decanediol with aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, cortic acid, azelaic acid, and sebacic acid, or with aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, e.g., in the form of a succinic, glutaric, and adipic acid mixture. For the production of polyester polyols, it may be advantageous to use the corresponding dicarboxylic acid derivatives instead of dicarboxylic acids, such as...Carboxylic acid diesters with 1 to 4 carbon atoms in the alcohol residue, carboxylic acid anhydrides, or carboxylic acid chlorides are to be used. Examples of polyhydric alcohols include glycols with 2 to 10, preferably with 2 to 6, carbon atoms, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propanediol, and dipropylene glycol. The polyhydric alcohols can be used alone or optionally in mixtures with each other. The polyester polyols further advantageously have molecular weights between about 400 and about 10,000 g / mol, preferably between about 600 and about 5,000 g / mol.

[0021] Furthermore, polycarbonate-based polyurethane elastomers, for example, are suitable thermoplastic polymers with shape memory and / or thermoresponsive properties for the programming tool. In this case, the diol used for the soft segments or switching segments in a thermoplastic polyurethane elastomer is preferably substantially completely or partially substituted by a polycarbonate having hydroxyl end groups, i.e., by a polycarbonate diol, which is obtained from the reaction of a diol, in particular from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and 1,10-decanediol, with diaryl carbonates, such as diphenyl, diitolyl, dixylyl, dinaphthyl carbonate, dialkyl carbonates, such as diethyl, dipropyl, dibutyl, diamyl, dicyclohexyl carbonate, Dioxolanones, such asEthylene and propylene carbonate, hexanediol-1,6-bischlorocarbonate, phosgene, or urea can be obtained. Furthermore, polycaprolactones, polyglycolides, and / or polyhydroxyalkanoates, preferably with a molar mass between approximately 400 g / mol and approximately 4000 g / mol, can preferably be used for the soft or switching segments in such polycarbonate-based polyurethane elastomers.

[0022] Furthermore, particularly in thermoplastic polyurethane elastomers with shape memory and / or thermoresponsive properties, the chain extender diol can be partially substituted by a diamine. Examples of this include isophorone diamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-1,3-propylenediamine, N,N'-dimethylethylenediamine, and aromatic diamines such as 2,4-toluenediamine and 2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine, and / or 2,6-toluenediamine, as well as primary ortho-, di-, tri-, and / or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes. The aforementioned diamines can be used individually or in any mixture with one another. Diamines as sole chain extenders are generally not suitable, as the resulting polyureas cannot be processed thermoplastically or exhibit insufficient shape memory properties.

[0023] If the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is a thermoplastic polymer, an advantageous embodiment of the method according to the invention provides that the programming tool is produced by melt layers by plasticizing the at least one first thermoplastic polymer with shape memory properties and / or with thermoresponsive properties and depositing it layer by layer to form the programming tool by means of at least one nozzle of a controlled movable print head of a 3D printer.Such fused deposition modeling (FDM) or fused filament fabrication (FFF) processes using 3D printers are well-known and represent manufacturing processes in which one or more filaments made of at least one (thermoplastic) polymer with shape memory and / or thermoresponsive properties are plasticized in a plasticizing unit of the 3D printer and deposited layer by layer through an exit nozzle typically located in the print head of the 3D printer. This process creates the programming tool ultimately formed from a multitude of such layers or "droplets." This enables the layer-by-layer production of relatively complex components, suitable for prototyping or small-batch production, which would otherwise be difficult to manufacture using conventional thermoplastic processing methods such as injection molding, extrusion, etc., programming tools that are difficult or impossible to manufacture, whereas the fused deposition modeling (FDM) process can also be used for the mass production of programming tools with relatively complex geometries or surface structures. In the FDM process, also known as "additive manufacturing" 3D printing, a three-dimensional model of the programming tool to be produced is typically created digitally, which can be done using well-known methods of computer-aided design (CAD). Furthermore, suitable software, such as a slicer program (e.g.,Cura™ or similar software) decomposes the three-dimensional model of the programming tool to be produced into a plurality of thin layers, whereupon the plasticized, at least one first polymer with shape memory properties and / or thermoresponsive properties is deposited layer by layer via the nozzle of the correspondingly moving printhead to build up the programming tool layer by layer. Immediately after the polymer plasticizer, which is dispensed more or less in strands or droplets from the nozzle of the printhead, the curing process—or more precisely, the solidification process—begins, whereby the deposited plasticizer solidifies, for example, at ambient temperature or under active cooling (see, for example, DE 10 2018 003 273 A1).

[0024] The programming of the programming tool thus produced, from its first to its second form, can then be carried out in a conventional manner after its actual manufacture, by thermomechanically treating the printed programming tool to transform it into a desired (second) form, from which it can then be returned to its original (first) form when the programming tool is heated to the switching temperature of its at least one first (thermoplastic) polymer with shape memory and / or thermoresponsive properties.

[0025] Alternatively or additionally, some shape changes of the programming tool, such as shrinking from its first shape to its second shape, can also be preset, in particular by selecting the printing parameters of the 3D printer, such as the nozzle temperature of the print head or the temperature of the polymer plasticizer, whereby the shape change is more pronounced the smaller the difference between the nozzle temperature of the print head and the switching or glass transition temperature of the first polymer with shape memory properties and / or with thermoresponsive properties.If the at least one first (thermoplastic) polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is heated in the plasticizing unit and, in particular, in the extrusion nozzle of the 3D printer to a maximum temperature below the melting transition temperature range of its hard segments, so that the hard segments are not completely melted, and if the at least one first (plasticized thermoplastic) polymer with shape memory properties and / or with thermoresponsive properties is ejected from the extrusion nozzle of the 3D printer, formed into the programming tool, and cooled to a temperature below the switching or glass transition temperature range, then the at least one first (thermoplastic) polymer with shape memory properties and / or with thermoresponsive properties of the programming tool can be programmed together with its creation, i.e.,During its shaping process, it is formed into a first shape by melt layers, from which it can later be transformed into its second shape when the at least one first (thermoplastic) polymer with shape memory and / or thermoresponsive properties is heated at least to, or expediently above, its switching temperature, but below the melting transition temperature range of its hard segments. The programming tool thus exhibits functional integration in the sense of thermoresponsiveness. In this context, reference is also made to DE 10 2019 007 939 A1, which is hereby explicitly incorporated into the present disclosure.

[0026] If the programming tool is created, in particular, by fused layers, it is therefore possible that the degree of deformation of the at least one first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool differs between its first shape and its second shape. - by adjusting and / or changing the printing parameters of the 3D printer, and / or - controlled by the use of different first polymers with shape memory properties and / or thermoresponsive properties during the melt layering of the programming tool.

[0027] As mentioned above, the shape recovery behavior between the first shape and the second shape of the programming tool can be controlled by the temperature set in the plasticizing unit and / or in the exit nozzle of the 3D printer, as well as by the geometry of the exit nozzle and / or by the pressure set inside the plasticizing unit, the former ensuring the incomplete melting of the hard segments of the at least one first polymer with shape memory properties and / or with thermoresponsive properties, while the latter allows mechanical forces of different magnitudes and / or directions to be introduced into the not completely melted polymer material.Furthermore, it becomes possible to process two or more first (thermoplastic) polymers with shape memory and / or thermoresponsive properties, which may, for example, have different glass transition temperatures of their soft segments and / or their mixed phases of soft and hard segments, or different switching temperatures, together into the programming tool. In this way, it is possible, on the one hand, to precisely adjust the switching temperatures for the phase transitions of the first polymers with shape memory and / or thermoresponsive properties of the programming tool. On the other hand, alternatively or additionally, by influencing the heat transfer in different areas of the programming tool, a time-dependent switching, i.e., a time-dependent, area-specific deformation of the programming tool from the manufacturing-induced first shape to the second shape, can be triggered.For these purposes, polymer blends or polymer mixtures of primary (thermoplastic) polymers with shape memory and / or thermoresponsive properties can be used, or several printing filaments made of different polymers can be employed in melt layer printing (so-called "multi-material printing"), whereby at least one or all of these polymers are (thermoplastic) polymers with shape memory and / or thermoresponsive properties. In this way, broad variations in the desired shape-changing capability of the programming tool are possible, whereby, in particular, different shape changes of varying degrees can be programmed locally or regionally, which are then transferred to the polymer molded part during programming.

[0028] According to an advantageous further development, it can be provided that at least one first polymer with shape memory properties and / or thermoresponsive properties of the programming tool is combined with at least one additive. While the additives can, in principle, be any known additives, such as dyes, pigments, fillers, lubricants, plasticizers, antioxidants, UV stabilizers, matting agents, reinforcing agents, flame retardants, antistatic agents, hydrolysis stabilizers, impact modifiers, and the like, the additive can, in particular, be selected from the group of electrically conductive and / or thermally conductive and / or magnetic, particulate and / or fibrous fillers. For example, the use of thermally conductive fillers, such as...Graphite, graphene, carbon black, carbon fibers or powders, and the like can be used to shorten switching times when the programming tool is transferred from its manufacturing-imparted first form to its second form for programming the polymer molded part. Furthermore, the polymer matrix of the resulting programming tool can be functionalized by using such fillers to generate heat under the influence of external factors such as electric current, magnetic fields, or electromagnetic radiation, e.g., in the infrared, ultraviolet, or microwave spectrum, provided that the metallic or carbon-based fillers possess inductive or radiation-absorbing properties. Advantageous fillers can therefore, for example, have a graphene structure, such as that found in...The filler material can be found in graphite, carbon nanotubes (CNTs), graphene flakes, or expanded graphite. Other fine particles with a nanoscale dimension can also be used as auxiliary materials or fillers. Examples include magnetic nanoparticles, ferromagnetic particles, especially NiZn particles, iron oxide particles, and magnetite particles. Nanoclays can also be used as fillers. These nanoclays can be based on silicon nitride, silicon carbide, silicon oxide, zirconium oxide, and / or aluminum oxide. Other possible fillers include oligomeric silsesquioxanes, graphite particles, graphene, carbon nanotubes, and also fine metal particles. Combinations of such filler materials can, of course, also be used.Furthermore, it should be mentioned at this point that, of course, at least one second polymer with shape memory and / or thermoresponsive properties of the polymer molded part programmed by means of the programming tool according to the invention can also contain such fillers, including those which are suitable for adjusting the mechanical, electrical, magnetic and / or optical properties of the polymer molded part and adapting them to the respective application.

[0029] As already indicated, at least one second polymer of the polymer molded part can be one from the group of, in particular thermoplastic, compact or foamed one-way or two-way shape memory polymers, whereby the polymers or polymer blends with shape memory properties and / or with thermoresponsive properties mentioned above in relation to the programming tool are also generally suitable for the polymer molded part.

[0030] Furthermore, the inventive method makes it possible to program at least one polymer molded part which contains at least two different second polymers with shape memory properties and / or with thermoresponsive properties with different properties, such as those of the type mentioned above.

[0031] According to a further development of the inventive method, it can also be provided that the at least one polymer molded part made from the at least one second polymer with shape memory properties and / or with thermoresponsive properties is programmed in the presence of at least one further molded part, wherein the at least one polymer molded part made from the at least one second polymer with shape memory properties and / or with thermoresponsive properties is joined from its first form to its second form, in particular to the further molded part, during programming. The further molded part can itself be a polymer molded part, e.g. made from at least one second polymer with shape memory properties and / or with thermoresponsive properties or also from conventional polymers, or molded parts made from any other materials, such as metal, ceramic, glass, stone, wood, etc., which are mechanically connected to at least one second polymer with shape memory properties and / or thermoresponsive properties by transferring at least the polymer molded part from its first shape into its second shape during its programming, so that, for example, the further molded part is again detached from the programmed polymer molded part made from at least one second polymer with shape memory properties and / or thermoresponsive properties when the latter is heated to its switching temperature in order to transfer it from its second shape back into its first shape.

[0032] Furthermore, the method according to the invention can be used for programming virtually any polymer molded parts made of polymers with shape memory properties and / or with thermoresponsive properties, whereby, in addition to the application areas mentioned above, polymer molded parts in the form of, for example, - smart technical components, such as gears and gears with inherent overheating protection, - Seals and connecting pieces, as well as insulating elements, in particular those made of foamed shape memory polymers, which, for example, lead to increased sealing / thermal insulation when the temperature rises to the switching temperature due to a change in shape, - self-folding and / or self-erecting structures, e.g. for use in aerospace, biomedicine or the like, - self-assembling and / or self-repairing systems, e.g. for construction, for use in harsh environments or the like, - self-disassembling objects which, for example, have anchoring elements that contract at least partially as soon as the shape memory effect is triggered, - Microcomponents of any kind, - Multifunctional objects, e.g. for use in biomedicine, robotics or the like, - shape-changing switches, sensors or actuators for virtually any technical application, etc.

[0033] Further features and advantages of the invention will become apparent from the following description of exemplary embodiments with reference to the drawings, in which the at least one first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is designated by “FGP1” and the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part to be programmed is designated by “FGP2”. The drawings show: Fig. 1 to 4 each highly schematic perspective views of different embodiments of a programming tool made of a first shape memory polymer “FGP1” in its first form (left) and in its second form, after it has been heated at least to the switching temperature of the first shape memory polymer (center), as well as a polymer molded part made of a second shape memory polymer “FGP2” programmed into its second form with this tool (right); Fig. 5 a highly schematic perspective view of an embodiment of a programming tool made from two different first shape memory polymers “FGP1a” and “FGP1b”; Fig. 6 and Fig. 7 highly schematic perspective views of different embodiments of a programming tool consisting of a first shape memory polymer “FGP1” in its first form (left), a polymer molded part to be programmed with it consisting of a second shape memory polymer “FGP2” in its first form (middle left), the polymer molded part inserted into a mold space of the programming tool still in its first form, which is also still in its first form “FGP2 in FGP1” (middle right), and the programming tool switched to its second form with the polymer molded part programmed in its second form in this way (right); Fig. 8 a highly schematic perspective view of an embodiment of a programming tool consisting of a first shape memory polymer “FGP1” in its first form (left), a polymer molded part to be programmed with it consisting of two different second shape memory polymers “FGP2a” and “FGP2b” in its first form (middle left), the polymer molded part inserted into a mold space of the programming tool still in its first form, which is also still in its first form “FGP2 in FGP1” (middle right), and the programming tool switched to its second form with the polymer molded part programmed in this way into its second form (right); Fig. 9 a highly schematic perspective view of an embodiment of a programming tool consisting of a first shape memory polymer “FGP1” in its first form (left), a polymer molded part to be programmed with it consisting of a second shape memory polymer “FGP2” in its first form (middle left), the polymer molded part inserted into a mold space of the programming tool still in its first form, which is also still in its first form “FGP2 in FGP1” (middle), the programming tool switched to its second form with the polymer molded part programmed in this way into its second form (middle right), and the polymer molded part programmed into its second form after it has been cooled to its mold fixing temperature and removed from the programming tool (right); Fig. 10 A highly schematic perspective view of an embodiment of a programming tool consisting of a first shape memory polymer “FGP1” in its first form (left), a polymer molded part to be programmed with it consisting of two different second shape memory polymers “FGP2a” and “FGP2b” in its first form (middle left), the polymer molded part inserted into a mold space of the programming tool still in its first form, which is also still in its first form “FGP2 in FGP1” (middle), the programming tool switched to its second form with the polymer molded part programmed in this way into its second form (middle right), and the polymer molded part programmed into its second form after it has been cooled to its mold fixing temperature and removed from the programming tool (right); Fig. 11 a highly schematic perspective view of an embodiment of a programming tool made of two different first shape memory polymers “FGP1a” and “FGP1b” in its first form (left), a polymer molded part to be programmed with it made of a second shape memory polymer “FGP2” in its first form (middle left), the polymer molded part inserted into a mold space of the programming tool still in its first form, which is also still in its first form “FGP2 in FGP1” (middle), the programming tool switched to its second form with the polymer molded part programmed in this way into its second form (middle right), and the polymer molded part programmed into its second form after it has been cooled to its mold fixing temperature and removed from the programming tool (right); Fig. 12A a photographic view of, on the one hand, an embodiment of a programming tool made of a first shape memory polymer in its first form substantially corresponding to the Fig. 6 (right) and a polymer molded part to be programmed herewith from a second shape memory polymer in its first form, also essentially according to the Fig. 6 (left); Fig. 12B a photographic view of the programming tool in its initial form within the form space according to Fig. 12A used polymer molded part, which is also still in its first form; Fig. 12C several photographic views of the form space of the programming tool according to Fig. 12A and Fig. 12B inserted polymer molded part during the programming of the same, during which the programming tool is heated to the switching temperature (here: of about 75°C) of its first shape memory polymer in order to switch the programming tool from its first form to its second form and in this way to program the polymer molded part from its first form to its second form; Fig. 12D a photographic view of the polymer molded part to be programmed according to Fig. 12A and Fig. 12B with another molded part, with which it was programmed using the programming tool according to Fig. 12A and Fig. 12B should be connected; Fig. 12E a photographic view of the polymer molded part connected to the further molded part according to Fig. 12D, after it was done using the programming tool according to Fig. 12A and Fig. 12B has been programmed from a first form into its second form; Fig. 13A a photographic view of an embodiment of a programming tool made of a first shape memory polymer in its first form; Fig. 13B a ​​photographic view of a by means of the programming tool according to Fig. 13A to programmable polymer molded part from a second shape memory polymer in its first form; Fig. 13 C a photographic view of the programming tool in its initial form within the form space according to Fig. 13A used polymer molded part, which is also still in its first form according to Fig. 13B; and Fig. 13D one of the Fig. 13C corresponding photographic view of the form space of the programming tool according to Fig. 13A polymer molded part used according to Fig. 13B, after the programming tool has been heated to the switching temperature of its first shape memory polymer in order to switch it from its first shape to its second shape and thus program the polymer molded part from its first shape to its second shape.

[0034] In the Fig. 1 to 4 are Fig. Figures 1 to 4 show schematic views of different embodiments of a programming tool made from a first shape-memory polymer FGP1. The tool is shown on the left in its first form, which is created, for example, by means of fused layers during manufacturing, as explained in detail above. The middle view shows the programming tool in its second form, into which it has been switched after being heated to at least the switching temperature of its first shape-memory polymer. The programming tool according to the Fig. Models 1 to 4 differ primarily in the contour of their mold space, which in the present cases, for example, has various cylindrical configurations and in the Fig. 3 is provided with radial openings. The programming tools of the Fig. Figures 1 to 4 are, for example, formed from two symmetrical programming tool halves, each enclosing approximately half of its form space, and are essentially extended axially during the switching process from their first form to their second. In the respective right-hand views of the Fig. Figures 1 to 4 show a polymer molded part made of a second shape-memory polymer FGP2, programmed into its second shape, after it has been removed from the programming tool (center) after being switched into its second shape, having previously been cooled to its mold fixing temperature. The switching temperature of the second shape-memory polymer FGP2 of the polymer molded part is preferably greater than or equal to the switching temperature of the first shape-memory polymer FGP1 of the programming tool, to ensure that while the programming tool is heated to the switching temperature of its first shape-memory polymer FGP1, the second shape-memory polymer FGP2 of the polymer molded part is also heated to its switching temperature in order to program it into its second shape.If the polymer molded part programmed in this way is heated again to the switching temperature of its second shape memory polymer FGP2, it is returned from the second mold (on the right) to its first mold (into the . Fig. (1 to 4 not shown graphically) switched, thus reversing the programmed shape change, whereby in the present case it essentially shrinks in the axial direction.

[0035] As can be seen from the Fig. 5, the programming tool can also be made from two or more different first shape memory polymers FGP1a and FGP1b, for example to provide for different switching temperatures and / or different shape changes when it is switched from its first shape to its second shape by heating it to the respective switching temperature of the first shape memory polymers FGP1a, FGP1b, in order to (in the Fig. 5 (not shown) to program the polymer molded part from its first shape into its second shape.

[0036] In the Fig. 6 and Fig. Figure 7 shows schematic views of embodiments of a programming tool made of a first shape-memory polymer FGP1, which is shown on the left in its first form. This form is created, for example, by means of fusion layers during manufacturing, as described in detail above. In this case, the programming tool is, for example, formed in one piece and essentially shaped like a ring, which defines a cylindrical—here approximately circular—mold space inside. On the left center of each figure are various embodiments of polymer mold parts made of a second shape-memory polymer FGP2, which are to be programmed by means of the programming tool. These parts are shown in their first form and have an outer contour that is essentially complementary to the inner contour of the programming tool in its first form, and is also cylindrical in this case.In this case, the respective polymer molded part exhibits a (. Fig. 6) or more ( Fig. 7) Through-holes. In the middle right-hand view, the polymer molded part, still in its first form, has been inserted into the programming tool. If the programming tool is now heated to at least the switching temperature of its first shape-memory polymer, it switches back into its second form, whereby this shape change is transferred to the polymer molded part in order to program it from its first form to its second form (see the right-hand view). For the aforementioned reasons, the switching temperature of the second shape-memory polymer FGP2 of the polymer molded part is preferably greater than or equal to the switching temperature of the first shape-memory polymer FGP1 of the programming tool. The polymer molded part, now converted into its second form, can then be cooled to the shape-fixing temperature of its second shape-memory polymer FGP2 and removed from the programming tool.The shape change transferred to the polymer molded part during its programming by the programming tool primarily involves shrinkage, reducing the cross-section of the programming tool's mold space, for example, by closing the through-hole(s). When the polymer molded part, programmed in this way, is heated back to the switching temperature of its second shape-memory polymer, FGP2, it switches from the second mold (on the right) back to its first mold (center left), thus reversing the programmed shape change. In this case, it essentially expands circumferentially, and the through-hole(s) reopen.

[0037] As from the Fig. As can be seen in Figure 8, the polymer molded part can also be formed from two or more different second shape memory polymers FGP2a and FGP2b, which, for example, have different switching temperatures, so that after programming the polymer molded part (see the right-hand figure of the Fig. 8) a successive reshaping of the polymer molded part takes place when it is first heated to the lower switching temperature, e.g. of the second shape memory polymer FGP2a, and then to the higher switching temperature, e.g. of the second shape memory polymer FGP2b.

[0038] In the Fig. Figure 9 shows schematic views of a programming tool formed from a first shape memory polymer FGP1 and of a polymer molded part made from a second shape memory polymer FGP2 programmed with it, which differ from those of the Fig. 6 and Fig. 7 primarily differ by a different (first and second) shape, whereby the polymer molded part is programmed here by means of the programming tool from its first shape (middle left) into its stretched second shape (right), whereby during the programming openings of the polymer molded part can also be closed.

[0039] The embodiment according to the Fig. 10 differs from that of the Fig. 9 in particular by the fact that - in this respect similar to the above Fig. 8 - the polymer molded part is formed from two or more different second shape memory polymers FGP2a and FGP2b, so that the polymer molded part programmed into its second shape (right) can successively undergo various shape changes when heated to the respective switching temperature of the respective second shape memory polymer FGP2a, FGP2b, whereby, for example, the programmed shape change of the polymer molded part itself is reversed, as is an imprint, which is symbolized by the letter “A” as an example.

[0040] In the case of Fig. 11 is the programming tool - similar in that respect to the one above. Fig. 5 - manufactured from two or more first shape memory polymers FGP1a and FGP1b, for example by means of melt layers using different shape memory polymer filaments, as explained in detail above. In this way, it is particularly possible, for example, to provide for different switching temperatures and / or section-by-section different shape changes of the programming tool when it is switched from its first shape to its second shape by heating it to the respective switching temperature of the first shape memory polymers FGP1a, FGP1b, in order to program the polymer molded part from its first shape (center left) to its second shape (right).

[0041] In the Fig. 12A is a photographic view of one similar to the above. Fig. 6 designed programming tools from a first shape memory polymer in its first form (right), on the other hand one similar to the above Fig. 6 designed, programmable polymer molded part made from a second shape memory polymer in its first form (left), shown in the photographic view of the Fig. 12B has been inserted into the form space of the programming tool, which has an inner contour that is essentially complementary to the outer contour of the polymer molded part. Fig. Figure 12 shows several photographic views of the polymer molded part inserted into the mold space of the programming tool during its programming. During this process, the programming tool is heated to at least the switching temperature of its first shape-memory polymer, which in this case is approximately 75°C, in order to switch the programming tool from its first mold to its second mold and thus program the polymer molded part from its first to its second mold. The programming tool undergoes shrinkage, which is transferred to the polymer molded part, so that its, for example, star-shaped through-hole closes when it has been programmed into the second (shrunken) mold. As the Fig. As can be seen from 12D, it is also possible, for example, to connect the polymer molded part to be programmed with another molded part – here: made of a different material, such as metal or the like – which in this case, for example, has a shaft penetrating the through-opening of the polymer molded part located in the first mold, by pressing the shaft of the further molded part into the former through-opening in a force-fit and / or form-fit manner after the programming of the polymer molded part, when its through-opening has been closed in the second mold (see the Fig. 12E). If the assembly consisting of the polymer molded part programmed in this way and the further molded part connected to it – here: in the form of a hybrid component made of different materials – is heated again to the switching temperature of the second shape-memory polymer of the polymer molded part, it will be removed from its second shape ( Fig. 12E) into its first form ( Fig. 12D) switched back, thus reversing the programmed shape change, whereby the polymer molded part in the present case essentially expands in the circumferential direction and the through-hole opens, so that the further molded part is again detached from the latter after triggering the shape memory effect of the second shape memory polymer of the polymer molded part.

[0042] While in the Fig. 13A a photographic view of a similar to the Fig. The programming tool 12A (right) is reproduced in its first form from a shape memory polymer, shows the Fig. Figure 13B shows a photographic view of a polymer molded part to be programmed using such a programming tool, made from a second shape-memory polymer in its first form, which, for example, has a delicate structure consisting of a multitude of approximately hollow cylindrical structures. In the photographic view of the Fig. In step 13C, the polymer molded part, still in its initial form, was inserted into the mold space of the programming tool, which was also still in its initial form and had an inner circumference that was essentially complementary to the outer circumference of the polymer molded part. Fig. Figure 13D shows a photographic view of the polymer molded part inserted into the mold space of the programming tool, after the programming tool has been heated to at least the switching temperature of its first shape-memory polymer in order to switch it from its first mold to its second mold and thus program the polymer molded part from its first mold to its second mold, whereby the shape change again consists primarily of shrinkage under compression of the delicate structures of the polymer molded part. If the polymer molded part programmed in this way is heated again to the switching temperature of its second shape-memory polymer, it is removed from its second mold ( Fig. 13D) into its first form ( Fig.13B) switched back, thus reversing the programmed shape change, whereby in the present case the polymer molded part essentially expands in the circumferential direction and the delicate hollow structures are formed again.

Claims

[1] Method for programming at least one polymer molded part made of at least one second polymer with shape memory properties and / or with thermoresponsive properties, in which the polymer molded part is transferred from a first shape into a second shape by applying mechanical deformation forces, so that it can be switched back to the first shape when heated to the switching temperature of its at least one second polymer with shape memory properties and / or with thermoresponsive properties, characterized by that programming the polymer molded part includes the following steps: (a) Providing a - having a mold cavity or - a programming tool which can be inserted into a mold cavity of a mold and which is made of at least one first polymer with shape memory properties and / or with thermoresponsive properties and which is programmed such that it can be switched from a first shape to a second shape when the at least one first polymer with shape memory properties and / or with thermoresponsive properties is heated to its switching temperature; (b) - introducing the polymer molded part made of the at least one second polymer with shape memory properties and / or with thermoresponsive properties into the mold space of the programming tool, or - inserting the programming tool into the molding space of the molding tool and introducing the polymer molded part made of the at least one second polymer with shape memory properties and / or with thermoresponsive properties into the molding space of the molding tool; (c) heating the programming tool at least to the switching temperature of its at least one first polymer having shape memory properties and / or having thermoresponsive properties, wherein it is transferred from its first shape to the second shape in order to program the polymer molded part made of the at least one second polymer having shape memory properties and / or having thermoresponsive properties from its first shape to its second shape; and (d) removing the polymer molded part programmed into the second shape from the at least one second polymer with shape memory properties and / or with thermoresponsive properties - from the form space of the programming tool or - from the mold cavity of the mold. [2] Method according to claim 1, characterized bythat the at least one switching temperature of the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is selected to be greater than or equal to the at least one switching temperature of the second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding to be programmed, so that when the programming tool is heated to the switching temperature of its at least one first polymer with shape memory properties and / or with thermoresponsive properties according to step (c), the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding is also heated at least to its switching temperature in order to program it from its first shape into its second shape,after which at least the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding is cooled at least to its shape-fixing temperature. [3] Method according to claim 1, characterized bythat the at least one switching temperature of the first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is selected to be lower than the at least one switching temperature of the second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding to be programmed, so that when the programming tool is heated to the switching temperature of its at least one first polymer with shape memory properties and / or with thermoresponsive properties according to step (c), the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding is cold-formed in order to program it from its first shape into its second shape,after which at least the at least one second polymer with shape memory properties and / or with thermoresponsive properties of the polymer molded part is cooled, in particular at least to its shape-fixing temperature. [4] Method according to one of claims 1 to 3, characterized by that at least the at least one first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is selected from the group of thermoplastic polymers, in particular from the group of polyetherurethanes and polyesterurethanes. [5] Method according to claim 4, characterized bythat the programming tool is produced by melt layers in that the at least one first thermoplastic polymer with shape memory properties and / or with thermoresponsive properties is plasticized and deposited layer by layer by means of at least one nozzle of a controllably movable print head of a 3D printer to form the programming tool. [6] Method according to claim 5, characterized by that the degree of deformation of the at least one first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool between its first shape and its second shape - by setting and / or changing the printing parameters of the 3D printer; and / or - is controlled by the use of different first polymers with shape memory properties and / or with thermoresponsive properties during the melt layering of the programming tool. [7] Method according to claim 5 or 6, characterized by that at least the at least one first polymer with shape memory properties and / or with thermoresponsive properties of the programming tool is mixed with at least one additive, wherein the additive is selected in particular from the group of electrically and / or thermally conductive and / or magnetic, particulate and / or fibrous fillers. [8] Method according to one of claims 1 to 7, characterized by that at least the at least one second polymer of the polymer molding is selected from the group of, in particular, thermoplastic, compact or foamed one-way or two-way shape memory polymers. [9] Method according to one of claims 1 to 8, characterized by that at least one polymer molded part is programmed which contains at least two different second polymers with shape memory properties and / or with thermoresponsive properties. [10] Method according to one of claims 1 to 9, characterized by that the at least one polymer molded part made of the at least one second polymer with shape memory properties and / or with thermoresponsive properties is programmed in the presence of at least one further molded part, wherein the at least one polymer molded part made of the at least one second polymer with shape memory properties and / or with thermoresponsive properties is connected in particular to the further molded part during the programming from its first shape into its second shape.

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