DE102018005428A1 - Method and device for programming molded polymer parts from shape memory polymers - Google Patents

Abstract

A method and a device for converting polymer molded parts, which contain a polymer with shape memory properties and / or with thermoresponsive properties or consist entirely of it, are proposed from a permanent shape to a temporary shape, in that the polymer with shape memory properties and / or with thermoresponsive properties are programmed under the action of force. The invention provides that the polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of fluid pressure acting at least in regions on the polymer molded part. Here, the polymer with shape memory properties and / or with thermoresponsive properties can be programmed, for example, by means of a fluid flow acting at least in regions on the polymer molding or also by means of a fluid pressure difference applied to the polymer molding at least in regions.

Description

The invention relates to a process for converting polymer moldings which contain or consist entirely of at least one polymer with shape memory properties and / or with thermoresponsive properties, from a permanent shape to a temporary shape, in that the at least one polymer with shape memory properties and / or with thermoresponsive properties are programmed under the action of force. The invention further relates to a device suitable for carrying out such a method for transferring polymer moldings which contain or consist entirely of at least one polymer with shape memory properties and / or with thermoresponsive properties, from a permanent shape to a temporary shape, with at least one programming station, which is designed to program the at least one polymer with shape memory properties and / or with thermoresponsive properties under the action of force.

Shape memory polymers are polymers which usually consist of at least two polymer components or, in particular, of a polymer component with different segments. On the one hand, these are "hard" segments, which also act as network points. On the other hand, they are "soft" segments that connect the network points to each other and are also referred to as switching segments and are elastic at elevated temperatures (in this case they are in an amorphous form), while they are rigid at lower temperatures (they are in this case in partially crystalline or glazed form).

Polymers of this type can be programmed with regard to their shape by heating them in their permanent form to a temperature which corresponds at least to the so-called switching temperature at which the phase transition (glass transition or melt transition) of the soft or switching segments takes place. At such a temperature, the polymer is then shaped into a temporary shape, after which it is cooled to its so-called shape-fixing temperature, which corresponds to the crystallization temperature or glass transition temperature of the soft or switching segments and can be in the range of the switching temperature, but is usually at least somewhat lower , The soft or switching segments are then again in partially crystalline or glazed form, so that the shape is retained. This shape is only temporary insofar as when a “programmed” mechanically deformed shape memory polymer is heated to a certain temperature, namely to its switching temperature, the soft segments (switching segments) are converted back into their amorphous form so that they can do so the hard component (network points) can no longer counteract the induced restoring force and the shape memory polymer returns to its original, permanent shape, ie the mechanical deformation is "undone". Furthermore, there is often also the possibility of programming by cold working, in which the polymers are at a temperature below their switching temperature, e.g. at ambient temperature, are deformed from their permanent form into a temporary one and, if the mold fixing temperature is lower, are cooled to their mold fixing temperature. In this case, too, there is only a temporary deformation, as if it is heated again to at least the switching temperature, in order to convert it into the amorphous phase like soft segments (switching segments) and thereby relax the mechanical stresses induced by the cold deformation, a reshaping takes place ,

In addition to such a shape memory, thermoresponsive polymers can also have a temperature memory. This is understood to mean that when the shape memory effect is triggered, the shape recovery begins approximately at the temperature at which the mechanical deformation was previously introduced into the polymer material. Such material behavior is exhibited, for example, by polymers with semicrystalline network structures, such as thermoplastic polyurethane elastomers ( N. Fritzsche, T. Pretsch in Macromolecules 47, 2014, 5952-5959 ; N. Mirtschin, T. Pretsch in RSC Advances 5, 2015, 46307-46315 ).

Furthermore, polymers with shape memory properties and / or with thermoresponsive properties are known which have two-way shape memory properties and can therefore be switched thermoreversibly, the switching segments of such shape memory polymers having a two-way shape memory effect undergoing a change in shape in the transition between their primarily crystalline state and their predominantly amorphous state , so they can be switched back and forth between their permanent form and their temporary form by cooling the polymer to the crystallization temperature, on the other hand by heating the polymer in the switching temperature range, ie the correspondingly programmed polymer deforms back and forth automatically when the temperature is controlled accordingly. Such polymers are e.g. from T. Pretsch, M. Bothe: "Bidirectional actuation of a thermoplastic polyurethane elastomer", Journal of Materials Chemistry A, 2_0 (2013), 14.491-14.497.

Fields of application for such polymers with shape memory properties and / or with thermoresponsive properties exist, for example, in various medical applications including bandages, compresses, insoles, artificial muscles and the like, but also in technical applications including micromechanical systems, actuators, such as in the form of switches for and / or shutdown of safety-relevant mechanical as well as electrical or electronic systems, brackets, spindles, locking devices, drive systems, active surfaces or in heat engines for converting thermal into kinetic energy and for temporarily storing thermal energy. Further areas of application for such polymers are in consumer articles, such as dishes, toys, pacifiers, textiles, in particular in functional textiles, for example for medical or sporting uses, mattresses, tubes and the like. Another interesting area of application for polymers with shape memory and / or with thermo-responsive is in the field of information carriers for counterfeit-proof labeling of goods in order to check their authenticity, one taking advantage, for example, of a machine-readable and / or otherwise optically clearly identifiable, code only becomes visible or readable when the information carrier made from such polymers is heated to its switching temperature, so that the polymer returns from its temporary form to its permanent form after it has previously been reset using the above described programming has been (temporarily) deformed. After they have been processed, such molded polymer parts, such as information carriers or any other shaped parts of the aforementioned type, such as, for example, the type mentioned above, namely have a shape and / or temperature memory, and in addition to thermoresponsiveness, thermochromic properties can also be provided, for example , provided the polymer molding has been printed or mixed with appropriate thermochromic dyes or pigments. In the case of information carriers, the authenticity can then additionally be verified by means of a color change at the corresponding color change temperature; in the case of any other molded parts, a special effect is achieved. Properties can also be produced, for example, by means of luminescent pigments, which can be desirable from an aesthetic point of view and, in particular, are also difficult to reproduce, so that in the case of polymer molded parts in the form of information carriers they ensure even greater protection against forgery. In addition, such molded polymer parts can also be admixed with magnetoresponsive or electroactive additives, in particular in fine particulate form, or these can be applied to them, which in particular can ensure a further security feature in that an information carrier designed in this way, for example, a change in shape caused by inductive heating shows after its polymer matrix from the polymers with shape memory properties and / or with thermoresponsive properties has been mixed with and / or coated with such additives and then programmed.

The main problem of such functional or multifunctional material systems, which contain at least one polymer with shape memory and / or with thermoresponsive properties or are formed entirely therefrom, is currently that both their production and, in particular, their programming is complex and expensive, which is why they have so far found little use in practice. In the prior art (cf. e.g. T. Pretsch, M. Ecker, M. Schildhauer, M. Maskos in J. Mater Chem. 22, 2012, 7757-7766 ; N. Fritzsche, T. Pretsch in Macromolecules 47, 2014, 5952-5959 ; M. Ecker, T. Pretsch in RSC Advances 4, 2014, 286-292 ; M. Ecker, T. Pretsch in RSC Advances 4, 2014, 46680-46688 ) Various methods for the production of prototypes of molded parts from polymers with shape memory properties and / or with thermoresponsive properties are described, which include different, often very time-consuming process steps. For example, approximately 2 mm thick platelets of shape memory polymers serve as the starting basis for the production of information carriers designed as labels, which are provided with a graphic code by means of various coloring processes, the coloring processes being based on the one hand on diffusion processes in which a dye solution is incorporated into the The polymer matrix is diffused in and the solvent is subsequently evaporated, or the platelets made from the shape memory polymer are coated with solutions or pastes made from the same shape memory polymer. In order to obtain a multifunctional material system, thermochromic dyes can be used (see also DE 10 2011 054 925 A1 ). After the coloring, an engraving, in particular by means of a carbon dioxide laser, is applied to the colored surface of the platelets from the shape memory polymer, after which the thermomechanical treatment is carried out by means of a tensile testing machine in a thermal chamber in order to deform the shape memory polymer above its switching temperature and then down to it cool its mold fixing temperature in order to program it with regard to its (temporary) shape. In addition to counterfeit-proof labeling of goods, the monitoring of cold chains is also proposed as a potential area of use for such information carriers ( N. Fritzsche, T. Pretsch in Macromolecules 47, 2014, 5952-5959 ; see. also DE 10 2014 104 901 A1 ), the switching temperature of the shape memory polymer in this case being in a range which must not be exceeded to ensure an uninterrupted cooling chain.

In addition to the individual, relatively complex process steps, it has also proven to be problematic that the morphological properties of the polymers used with shape memory properties and / or with thermoresponsive properties depend essentially on how much time passes before the respective further processing, in particular programming, the platelets used come from shape memory polymers in a subsequent process step.

On a laboratory scale, the programming of molded polymer parts with or from polymers with shape memory and / or with thermoresponsive properties is currently usually done in that the molded part, which is in its permanent shape, is programmed to be held in a temperature-controlled environment, such as in a temperature chamber with one for holding of the polymer molded part serving clamping device is individually deformed into a temporary shape. If the temperature chamber is equipped with a universal test system, a chamber volume that is large in relation to the dimensions of the polymer molded part must be tempered, which is associated with a comparatively high expenditure of time and money for programming; If a dynamic mechanical analysis (DMA) is subsequently carried out instead, the chamber volume required for tempering the polymer molded part on the basis of its programming can be kept smaller, but such programming is primarily only accessible to essentially thin, film-like molded parts. Such programming methods are therefore only suitable to a very limited extent for the series production of relatively large quantities and are used practically exclusively in research and development in order to ensure quantification of the shape memory properties, such as shape fixability, shape resettability, switching temperature etc.

In addition, applications of molded polymer parts with shape memory and / or with thermoresponsive properties are known, in which the programming of the polymer is done directly by the user, such as, for example, so-called rails commercially available under the trade name myTAP ™ for the treatment of snoring and sleep apnea , The transfer of the splint from its permanent shape into its temporary shape, adapted to the user, takes place individually in the mouth of the user after the latter has previously warmed the splint in hot water above the switching temperature of the polymer. In the mouth of the user, the splint is then cooled again below the mold fixing temperature of the polymer and the splint is held in the desired individual - temporary - shape in this way. In a similar way, commercially available pacifiers for babies made of shape memory polymers, for example under the trade name Luckydent ™, can first be heated in hot water above the switching temperature of the polymer, modeled and then fixed in cold water in their new individual - temporary - form.

In addition, polymer molded parts with shape memory properties and / or with thermoresponsive properties with very high viscoelasticity are used for so-called “one size fits all” applications, in which the polymer molded part is also brought into an individual shape by the user, but without being used program. Examples of such molded parts include bicycle saddles, shoe inserts and the like, in which the polymer molded part adapts to the desired shape solely on account of the good viscoelastic properties.

The DE 10 2015 014 291 A1 describes a process for the production of molded polymer parts from polymers with shape memory properties and / or with thermoresponsive properties, which lends itself to the large-scale production of molded parts from such polymers, in particular in the form of tamper-proof information carriers of the type mentioned above. The known method comprises the initial step of extrusion of a polymer with shape memory and / or with thermoresponsive properties as well as the immediately subsequent calibration of the extrudate to form an, in particular essentially film-shaped, continuous strand. In a subsequent step, the latter is at least partially deformed at a temperature which corresponds at least to the switching temperature of the polymer used with shape memory properties and / or with thermoresponsive properties, for example by applying a code, whereupon the at least partially deformed endless strand is cooled to the shape fixing temperature of the polymer used , Finally, the at least partially deformed endless strand is cut to length to obtain the polymer molded parts, such as, for example, film-shaped labels. The known method has proven to be advantageous for the more or less continuous production of such molded parts which are extrudable in their basic shape, but there are limits to the choice of molded part geometries.

The invention has for its object a method and a device for programming at least one polymer with shape memory and / or with thermoresponsive properties containing polymer moldings of the type mentioned with widely variable mold geometry for practically any application, including those of the above To propose a type which, at least largely avoiding the disadvantages mentioned above, ensures economical series production of such molded polymer parts.

In procedural terms, this object is achieved in a method of the type mentioned at the outset by programming the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of fluid pressure acting at least in regions on the polymer molding.

In terms of device technology, the invention also provides for achieving this object in a device of the type mentioned at the outset that the programming station has at least one device for supplying the at least one polymer with shape memory properties and / or with thermoresponsive properties with fluid pressure, in particular with gas pressure.

The configuration according to the invention, which is based on the generation of the deformation forces required for programming the at least one polymer with shape memory and / or with thermoresponsive properties of the polymer molded part by means of fluidic pressure, such as in particular gas or liquid pressure, proves both with regard to the expenditure on equipment and also in terms of energy efficiency as extremely inexpensive, since otherwise molding or pressing tools usually used for programming can be dispensed with. In addition, the invention is characterized by its versatility for practically any polymer materials, including polymer blends of one or more polymers with shape memory and / or with thermoresponsive properties, optionally with corresponding or other polymers (see below) and molded part geometries, such as for relatively thin polymer moldings with material thicknesses of less than about 100 nm up to material thicknesses of several millimeters, which can also optionally have any surface structures, such as in the form of elevations, depressions, recesses, cavities and the like. In addition, using conventional plastic processing methods such as Injection molding, hot pressing, extruding, calendering, casting, wet spinning, chemical or physical foaming etc., produced polymer moldings, e.g. scrims produced by electrospinning, 3D printed products or composites provided with fillers made of polymers with shape memory and / or with thermoresponsive properties, polymer networks in hybrid form, which have both switching segments and inorganic network points, multi-layer molded parts with at least one layer of polymers with shape memory and / or program in the manner according to the invention with thermoresponsive properties and information carriers of the type mentioned above, which are provided in the permanent form with a, preferably machine-readable, code. The same applies to both open-pore and closed-pore foams which contain at least one polymer with shape memory and / or with thermoresponsive properties or are formed entirely therefrom.

According to an advantageous embodiment of the method according to the invention, it can be provided that the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of a fluid flow, in particular a gas flow, which acts on the molded polymer part at least in regions. In this case, the force required to transfer the polymer molded part from its permanent shape into the desired temporary shape during programming is carried out by means of a fluid flow acting locally on the polymer molded part, such as preferably a gas stream, e.g. from air, inert gases, such as nitrogen, carbon dioxide, argon etc., other gases or gas mixtures or liquids, which lead to a defined local deformation of the same when it hits the polymer molding.

• - Art des verwendeten Fluides;
• - Auftreffwinkel des mittels der Düse erzeugten Fluidstromes auf das Polymer-Formteil (sei es durch Relativverlagerung des Polymer-Formteils in Bezug auf die Düse(n) und/oder sei es durch Relativverlagerung der Düse(n) in Bezug auf das Polymer-Formteil);
• - Auftreffgeschwindigkeit des mittels der Düse erzeugten Fluidstromes auf das Polymer-Formteil;
• - Abstand der Düse von dem Polymer-Formteil;
• - Querschnittsform der Düse, wie in Form einer Vollstrahl-, Flachstrahl-, Kegelstrahldüse oder dergleichen;
• - Geometrie wenigstens einer Aussparung einer das Polymer-Formteil tragenden Halteeinrichtung; und
• - Geometrie wenigstens einer Aussparung einer zwischen dem

Such a fluid flow is expediently generated by means of at least one or more nozzle (s), with at least one parameter from the group in particular being used to deform the polymer molded part at least in regions

• - type of fluid used;
• - Angle of incidence of the fluid flow generated by means of the nozzle onto the polymer molding (be it by relative displacement of the polymer molding in relation to the nozzle (s) and / or be it by relative displacement of the nozzle (s) in relation to the polymer molding) ;
• - Impact speed of the fluid flow generated by the nozzle on the polymer molding;
• - Distance of the nozzle from the molded polymer part;
• - Cross-sectional shape of the nozzle, such as in the form of a full jet, flat jet, cone jet or the like;
• - Geometry of at least one recess of a holding device carrying the polymer molded part; and
• - Geometry of at least one recess between the

Polymer molding and the nozzle arranged template can be adjusted according to the temporary shape of the polymer molding. In this way, the shape or the cross section of the fluid stream or steel, including its speed or intensity and direction, can be set precisely to the temporary shape of the polymer molding to be produced, it also being possible to separate between the polymer molding and a template for the nozzle, e.g. to be arranged in the manner of preforms, through the recesses of which the polymer molded part is exposed to the fluid stream or jet, while it is otherwise protected by the template against the action of the fluid stream. In a corresponding manner, it is also conceivable to provide a corresponding holding device which carries the polymer molded part during programming (see also below for this) with template-like recesses which serve the same purpose.

Furthermore, it can be expedient if the fluid stream acting on the polymer molding is loaded with particles, in particular with solid particles, but also with liquid particles, for example, in order to increase the intensity of the deformation forces exerted by means of the fluid stream or steel as required.

• - Art des verwendeten Fluides;
• - Auftreffwinkel des mittels der Düse erzeugten Fluidstromes auf das Polymer-Formteil;
• - Auftreffgeschwindigkeit des mittels der Düse erzeugten Fluidstromes auf das Polymer-Formteil;
• - Abstand der Düse von dem Polymer-Formteil;
• - Querschnittsform der Düse, wie in Form einer Vollstrahl-, Flachstrahl-, Kegelstrahldüse oder dergleichen;
• - Geometrie wenigstens einer Aussparung einer das Polymer-Formteil tragenden Halteeinrichtung; und
• - Geometrie wenigstens einer Aussparung einer zwischen dem Polymer-Formteil und der Düse angeordneten Schablone einstellbar ist.

In terms of device technology, it can accordingly be provided according to an advantageous embodiment that the device for supplying the at least one polymer with shape memory properties and / or with thermoresponsive properties with fluid pressure has at least one nozzle which can be connected, for example to a fluid pressure reservoir, a compressor or the like, for supplying the polymer Molded part with a fluid stream, in particular at least one parameter from the group

• - type of fluid used;
• - Impact angle of the fluid flow generated by the nozzle on the polymer molding;
• - Impact speed of the fluid flow generated by the nozzle on the polymer molding;
• - Distance of the nozzle from the molded polymer part;
• - Cross-sectional shape of the nozzle, such as in the form of a full jet, flat jet, cone jet or the like;
• - Geometry of at least one recess of a holding device carrying the polymer molded part; and
• - Geometry of at least one recess of a template arranged between the polymer molding and the nozzle is adjustable.

According to an advantageous embodiment of the method according to the invention, it can be provided that the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of a fluid pressure difference, in particular a gas pressure difference and / or possibly also a fluid pressure difference, applied to the polymer molded part at least in regions. In contrast to the fluid flow described above, in this case a more or less static pressure difference acts on the molded polymer part to apply force when programming, the latter being able to be arranged, for example, on an open side of at least one pressure chamber, so that inside the pressure chamber the pressure there and the ambient pressure on the side of the polymer molded part facing away from the pressure chamber or the pressure of a further pressure chamber which is also open on one side acts on the polymer molded part. At this point, it should be explicitly pointed out that “pressure” in the sense of the present disclosure does not necessarily refer to an overpressure compared to ambient pressure, but also a vacuum or vacuum. In a corresponding manner, the term “pressure chamber” in the sense of the present disclosure does not necessarily refer to an overpressure chamber, but also to a vacuum or vacuum chamber.

• - an einer Öffnung wenigstens einer Druckkammer angeordnet wird, welche mit einem gegenüber Umgebungsdruck unterschiedlichen (d.h. höheren oder geringeren) Fluiddruck beaufschlagt wird; oder
• - zwischen zwei einander zugewandten Öffnungen zweier Druckkammern angeordnet wird, welche mit unterschiedlichen Fluiddrücken beaufschlagt werden,

wobei zur zumindest bereichsweisen Verformung des Polymer-Formteils insbesondere wenigstens ein Parameter aus der Gruppe

• - Art des verwendeten Fluides;
• - Betrag der Fluiddruckdifferenz;
• - Geometrie wenigstens einer Aussparung einer das Polymer--Formteil tragenden Halteeinrichtung; und
• - Geometrie wenigstens einer Aussparung einer zwischen zumindest einer Seite des Polymer-Formteils und zumindest einer Druckkammer angeordneten Schablone, z.B. nach Art einer Präform,

entsprechend der temporären Form des Polymer-Formteils eingestellt wird.As already indicated, it can be provided in an advantageous embodiment in this context that the molded polymer part

• is arranged at an opening of at least one pressure chamber which is acted upon by a fluid pressure which is different (ie higher or lower) than the ambient pressure; or
• is arranged between two mutually facing openings of two pressure chambers, to which different fluid pressures are applied,

wherein for the at least partial deformation of the polymer molding, in particular at least one parameter from the group

• - Type of fluid used;
• - amount of fluid pressure difference;
• - Geometry of at least one recess of a holding device carrying the molded polymer part; and
• Geometry of at least one recess of a template arranged between at least one side of the polymer molded part and at least one pressure chamber, for example in the manner of a preform,

is set according to the temporary shape of the polymer molding.

Both in the dynamic pressurization of the polymer molded part described above by means of at least one nozzle and with the more or less static pressurization of the polymer molded part with a fluid pressure difference, the at least one polymer with shape memory can be used by means of the fluid pressure on the polymer molded part on the occasion of the programming thereof - And / or with thermoresponsive properties can be controlled or regulated by means of the aforementioned measures in such a way that the polymer molding is completely deformed, at least in some areas, ie the geometry of the molded polymer part is changed, or that e.g. only the surface of the molded polymer part is deformed at least in some areas, i.e. the surface structure is changed. The deformation can consequently be both primarily two-dimensional and in particular three-dimensional with precise adjustment of the degree of deformation. As a precaution, it should also be pointed out that the aforementioned design variants of generating a fluid pressure acting on the polymer molding during programming, be it dynamic in the form of a fluid flow or jet, or be it primarily static in the form of a fluid pressure difference between a pressure chamber and the environment or between two pressure chambers, of course for step-by-step or step-by-step programming, in particular of relatively complex molded part geometries, can also be combined with one another or can be carried out in several steps in succession in order to ensure gradual deformation on the occasion of the programming.

• - wenigstens zwei mit jeweils einer Öffnung versehene und mit unterschiedlichen Fluiddrücken beaufschlagbare Druckkammern, wobei das Polymer-Formteil zwischen den entgegengesetzt zueinander angeordneten Öffnungen positionierbar ist,

aufweist, wobei insbesondere wenigstens ein Parameter aus der Gruppe

• - Art des verwendeten Fluides;
• - Betrag der Fluiddruckdifferenz;
• - Geometrie wenigstens einer Aussparung einer das Polymer--Formteil tragenden Halteeinrichtung; und
• - Geometrie wenigstens einer Aussparung einer zwischen zumindest einer Seite des Polymer-Formteils und zumindest einer Druckkammer angeordneten Schablone, z.B. nach Art einer Präform,

entsprechend der temporären Form des Polymer-Formteils eingestellt wird.In terms of device technology, it can accordingly be provided according to the further advantageous embodiment that the device for supplying the at least one polymer with shape memory properties and / or with thermoresponsive properties with fluid pressure - at least one with an opening and one that is different from ambient pressure (e.g. higher or lower) ) Fluid pressure pressurized chamber (such as in the form of a pressure or vacuum chamber), wherein the polymer molding can be positioned in front of the opening; or

• at least two pressure chambers each provided with an opening and which can be acted upon with different fluid pressures, the polymer molded part being able to be positioned between the openings arranged opposite one another,

has, in particular at least one parameter from the group

• - type of fluid used;
• - amount of fluid pressure difference;
• - Geometry of at least one recess of a holding device carrying the molded polymer part; and
• Geometry of at least one recess of a template arranged between at least one side of the polymer molded part and at least one pressure chamber, for example in the manner of a preform,

is set according to the temporary shape of the polymer molding.

• - das Polymer-Formteil in seiner permanenten Form in einer Vorratsstation auf Vorrat gehalten und mittels der Handhabungseinrichtung an eine Programmierstation überführt wird, wo das wenigstens eine Polymer mit Formgedächtniseigenschaften und/oder mit thermoresponsiven Eigenschaften mittels des zumindest bereichsweise auf das Polymer--Formteil einwirkenden Fluiddruckes programmiert wird; und/oder
• - das Polymer-Formteil nach der Programmierung in seiner temporären Form von einer Programmierstation, wo das wenigstens eine Polymer mit Formgedächtniseigenschaften und/oder mit thermoresponsiven Eigenschaften mittels des zumindest bereichsweise auf das Polymer-Formteil einwirkenden Fluiddruckes programmiert worden ist, an eine Lagerstation überführt wird, um das programmierte Polymer-Formteil in der Lagerstation zwischenzulagern.

According to an advantageous development of the method according to the invention, it can be provided that the molded polymer part is taken at least on the occasion of programming the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of an, in particular automated, handling device, in particular

• - The polymer molding in its permanent form is kept in stock in a storage station and is transferred by means of the handling device to a programming station, where the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of the fluid pressure acting at least in regions on the polymer molding is programmed; and or
• after the programming, the polymer molding in its temporary form is transferred to a storage station from a programming station where the at least one polymer with shape memory properties and / or with thermoresponsive properties has been programmed by means of the fluid pressure acting on the polymer molding at least in some areas, to temporarily store the programmed polymer molded part in the storage station.

This results in particular in an efficient series programming of a plurality of polymer molded parts with at least one polymer with shape memory and / or with thermoresponsive properties in that the molded parts can be gripped by means of the, preferably automated, handling devices, for example in the form of a multi-axis industrial robot, an autosampler or the like, and fed to or removed from the programming station. While a plurality of non-programmable polymer moldings can be kept in stock in the storage station so that they can be successively fed to the programming station by means of the handling device, a plurality of polymer moldings that have already been programmed can be temporarily stored in the storage station after they have been the handling device have been transferred from the programming station to the storage station. Both the supply station and the storage station can be designed in a manner known per se, in the manner of stores, for example in the form of shelf stores, in each of which a plurality of - not yet programmed or already programmed - polymer molded parts in, e.g. The type and geometry of various polymer molded parts in an ordered or disordered manner, at least temporarily collected and transported to or from the programming station by means of the handling device.

The storage station can also, for example, at the end of a manufacturing process for the molded parts that have not yet been programmed, e.g. at the end of an extrusion, injection molding, pressing process or the like, whereby it is also possible by means of the storage station to combine several individually produced, not yet programmed polymer molded parts in groups in order to program them one after the other in a corresponding or different manner. Such groups of polymer moldings which have not yet been programmed can be positioned in the storage station at defined locations in order to enable targeted transfer to the programming station by means of the handling device, or they can also be more or less statistically in the storage station or in the sequence provided for programming be arranged, provided that the handling device has a correspondingly programmable control device, by means of which the removal of the desired type of molded polymer parts kept in stock can be predetermined in the desired order.

According to the invention, the programming station itself, which - as mentioned above - in particular comprises at least one nozzle and / or at least one pressure chamber open on one side, does not necessarily have to have an enclosure or any other physical delimitation from the environment, this of course to protect the operating personnel and the environment can also be provided.

• - eine Vorratsstation zur Bevorratung von Polymer-Formteilen in ihrer permanenten Form, von welcher die Polymer-Formteile mittels der Handhabungseinrichtung an die Programmierstation überführbar sind; und/oder
• - eine Lagerstation zur Zwischenlagerung von in ihre temporäre Form überführten Polymer-Formteilen, in welche die Polymer-Formteile mittels der Handhabungseinrichtung aus der Programmierstation überführbar sind,

umfasst.In terms of device technology, it can preferably be provided in this context that the device further comprises a, in particular automated, handling device, such as in the form of a multi-axis industrial robot, an autosampler or the like, for gripping the molded polymer part, the device further particularly

• - A storage station for storing polymer moldings in their permanent form, from which the polymer moldings can be transferred to the programming station by means of the handling device; and or
• a storage station for the intermediate storage of polymer moldings which have been converted into their temporary shape and into which the polymer moldings can be transferred from the programming station by means of the handling device,

includes.

In an expedient embodiment of the method according to the invention, the polymer molding can also at least on the occasion of programming the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of the handling device. As already mentioned, the handling device serves on the one hand for at least temporarily gripping polymer moldings, which have not yet been programmed and / or have already been programmed, in order to transfer them from the supply station to the programming station and / or from there to the storage station. On the other hand, the handling device can of course also be used for the temporary gripping of the polymer molded parts on the occasion of their programming, for example by the handling device during the action of the fluid flow or jet and / or during the exposure of a fluid pressure difference due to the arrangement at an opening of at least one pressure chamber being held. For this purpose, the handling device can be equipped with suitable suction or gripping devices, for example in the manner of tensioning devices, which are suitable for releasably fastening polymer molded parts to the handling device. In the latter case, a defined, preset torque for tightening clamping screws or nuts and / or a regulated, presettable hydraulic or pneumatic system can be used for releasably fixing the polymer molded parts on the handling device, by means of which the required holding force of the polymer can be used -Molded part can be adjusted.

According to an advantageous embodiment of the method according to the invention, the polymer molded part - as described above - can be gripped by means of the handling device at least on the occasion of programming the at least one polymer with shape memory properties and / or with thermoresponsive properties, wherein it is preferably transferred to at least one holding device which the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of the fluid pressure acting at least in regions on the polymer molded part, in particular a plurality of holding devices being provided, by means of which a plurality of polymer molded parts are programmed in succession. In this case, during the programming of a respective polymer molded part in a respective holding device, the handling device is again available for gripping another polymer molded part, be it for transferring it to another holding device for the purpose of programming or for removing a finished one programmed polymer molded part from a further holding device, so that the efficiency of the method according to the invention can be increased further.

According to an embodiment variant, in this connection it can be provided, for example, that several, for example at least three or more, holding devices are provided, each of which is equipped with a not yet programmed polymer molded part by means of the handling device (and from which the respective processed polymer molded part is preferably made is also removed again by means of the handling device), after which the holding devices equipped with a respective polymer molded part are successively fed to the programming station in order to program the polymer molded parts. In this way, while a polymer molded part located in a holding device is being programmed, a further, not yet programmed polymer molded part can be removed by means of the handling device, for example from the storage station, and added to a further holding device, and / or a further, already programmed polymer molded part can removed by means of the handling device from a further holding device and fed, for example, to the storage station. The holding devices can e.g. essentially connected to each other like a chain and / or arranged on a movable body, such as a conveyor, a turntable or the like. This opens up the possibility of a more or less continuous, automated programming of a plurality of molded polymer parts in succession.

Instead, it is also conceivable, for example, that two or more holding devices of the aforementioned type are arranged next to one another and are mounted such that they can be moved back and forth together in one direction and in the opposite direction. In this way, too, the polymer moldings accommodated in one of the holding devices can be transferred essentially continuously to the programming station and - after programming - away from it, with the handling device using at least one of the holding devices each with a polymer mold part that has not yet been programmed equipped and / or a fully programmed molded polymer part can be removed from one of the holding devices, while at least one polymer molded part located in a further holding device can be programmed in the programming station, which likewise results in high time efficiency with only a small space requirement.

As already explained, the holding devices can in particular be equipped with one or more cutout (s) adapted to the desired temporary shape of the programmed polymer molded part, by means of which the polymer molded part can be used to program the fluid pressure used to apply the deformation forces - be it in the form of a fluid flow or jet or be it in the form of a primarily static fluid pressure difference. In terms of construction, the holding devices can be designed essentially in the manner of frame-shaped frames into which a respective molded polymer part is inserted, inserted, clamped, or the like, in particular by means of the handling device. It may prove advantageous if the polymer molded part is fixed in the holding device at least locally, for example in the peripheral area thereof, for example non-positively, such as by clamping or the like, and / or positively, so that it is under the influence of the fluid pressure during programming maintains its fixed relative position with respect to the holding device and is not shifted relative to it. For the releasable fixing of a respective molded polymer part in a respective holding device, it is also conceivable, for example, that the holding device comprises two interconnected frame parts, between which a respective polymer molded part can be clamped, the frame parts of the holding device also correspondingly corresponding in this case, can have recesses adapted to the desired temporary shape of the polymer molded part, so that, on the occasion of the programming, the fluid pressure required for the deformation can act on the polymer molded part in some areas. In addition, the holding device can, for example, only comprise clamps, as are known as such, for example, in conventional clamping devices of machine tools, the latter being used, for example, when programming a polymer molded part Stencils of the type mentioned above can be covered, which in turn are provided with corresponding cutouts in order to expose the polymer molded part in areas to the fluid pressure necessary for the deformation on the occasion of the programming.

In terms of device technology, it can therefore preferably be provided that the device further has at least one holding device which is designed to hold the polymer molded part and into or from which the polymer molded part can be transferred by means of the handling device, in particular a plurality of holding devices being provided which can be transferred to the programming station one after the other. With regard to advantageous structural configurations of the holding devices, reference is made to the above explanations.

According to the method according to the invention, it can be provided, on the one hand, that the at least one polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding for programming it by means of the fluid pressure acting at least in regions on the polymer molding at a temperature which is lower than the switching temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties, for example at ambient temperature, is at least partially cold worked.

• - Erwärmung des zur Erzeugung des zumindest bereichsweise auf das Polymer-Formteil einwirkenden Fluiddruckes verwendeten Fluides,
• - Bestrahlung des Polymer-Formteils mit elektromagnetischer Strahlung, beispielsweise im ultravioletten Spektrum (UV), im Infrarot-Spektrum (IR) oder - sofern das Polymer mit Formgedächtnis- und/oder mit thermoresponsiven Eigenschaften selbst mikrowellenabsorbierend oder mit mikrowellenabsorbierenden Füll- und/oder Verstärkungsstoffen versetzt ist - im Mikrowellenspektrum (MW),
• - induktive Erwärmung des Polymer-Formteils, wie mittels eines hochfrequenten magnetischen Wechselfeldes, sofern das wenigstens eine Polymer mit Formgedächtnis- und/oder mit thermoresponsiven Eigenschaften mit elektrisch leitfähigen Füll- und/oder Verstärkungsstoffen versetzt ist,
• - Erwärmung einer das Polymer-Formteil tragenden Halteeinrichtung, beispielsweise mittels eines Widerstandsheizelementes oder insbesondere mittels eines Peltier-Elementes, welches auch eine Abkühlung des von der Halteeinrichtung getragenen Polymer-Formteils nach der Verformung ermöglicht, und/oder
• - Vorwärmung des Polymer-Formteils vor der Programmierung, z.B. in der Vorratsstation,

durchgeführt wird. Dabei ermöglicht das erfindungsgemäße Verfahren insbesondere dann, wenn das zur Ausübung eines Fluiddruckes auf das Polymer-Formteil anlässlich der Programmierung verwendete Fluid erwärmt und die Wärme zur Aufheizung des Polymer-Formteils zumindest auf die Schalttemperatur des wenigstens einen Polymers mit Formgedächtnis- und/oder mit thermoresponsiven Eigenschaften genutzt wird, oder wenn Infrarotstrahlung zur Erwärmung eines solchen Polymers auf dessen Schalttemperatur eingesetzt wird, eine sehr energieeffiziente und verlustarme Erwärmung. Neben den anderen vorgenannten Aufheizmethoden, wie beispielsweise einer indirekten Erwärmung durch Mikrowellenbestrahlung oder Induktionserwärmung mittels in das Formgedächtnispolymer eindispergierten, mikrowellenabsorbierenden und/oder elektrisch leitfähigen Füll- und/oder Verstärkungspartikeln oder -fasern, kommen selbstverständlich auch beliebige andere Heizmethoden in Betracht, wie z.B. eine (beispielsweise konvektive) Erwärmung der ein jeweiliges Polymer-Formteil zumindest anlässlich der Programmierung tragenden Halteeinrichtung oder eine Erwärmung des Polymer-Formteils durch wärmeleitenden Kontakt mit beheizten Folien, Textilien oder ähnlichen, vorzugsweise nachgiebigen Materialien, welche im Wesentlichen vollflächig oder bereichsweise mit dem Polymer-Formteil in wärmeleitenden Kontakt gebracht werden können. Zur Erhöhung der Zeiteffizienz kann alternativ oder zusätzlich zudem zumindest ein Teil der Vorratsstation beheizt werden, um diejenigen Polymer-Formteile, deren Formgedächtnispolymere als nächstes programmiert werden sollen, vorzuwärmen.Alternatively, the method according to the invention is also particularly suitable for the at least one polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding to be programmed by means of the fluid pressure acting at least in regions on the polymer molding at a temperature which is at least the switching temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties, is at least partially deformed, after which the polymer molding is cooled at least to the mold fixing temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties, the heating of the polymer molding at least to the switching temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties, in particular by means of

• Heating of the fluid used to generate the fluid pressure acting at least in regions on the polymer molding,
• - Irradiation of the molded polymer part with electromagnetic radiation, for example in the ultraviolet spectrum (UV), in the infrared spectrum (IR) or - provided the polymer with shape memory and / or with thermoresponsive properties is itself microwave-absorbent or with microwave-absorbent fillers and / or reinforcing materials is offset - in the microwave spectrum (MW),
• inductive heating of the molded polymer part, such as by means of a high-frequency alternating magnetic field, provided that the at least one polymer with shape memory and / or with thermoresponsive properties is mixed with electrically conductive fillers and / or reinforcing materials,
• - Heating of a holding device carrying the polymer molded part, for example by means of a resistance heating element or in particular by means of a Peltier element, which also enables cooling of the polymer molded part carried by the holding device after the deformation, and / or
• - preheating of the molded polymer part before programming, eg in the storage station,

is carried out. The method according to the invention enables, in particular, when the fluid used to exert a fluid pressure on the molded polymer part during the programming warms up and the heat for heating the molded polymer part at least to the switching temperature of the at least one polymer with shape memory and / or with thermo-responsive Properties is used, or if infrared radiation is used to heat such a polymer to its switching temperature, a very energy-efficient and low-loss heating. In addition to the other heating methods mentioned above, such as indirect heating by means of microwave radiation or induction heating by means of microwave-absorbing and / or electrically conductive filling and / or reinforcing particles or fibers dispersed into the shape memory polymer, any other heating methods are of course also possible, such as, for example, a ( for example convective) heating of the respective holding device carrying a respective polymer molded part at least on the occasion of the programming or heating of the polymer molded part by heat-conducting contact with heated foils, textiles or similar, preferably compliant materials which essentially cover the entire surface or areas of the polymer molded part thermally conductive contact can be brought. To increase the time efficiency, as an alternative or in addition, at least a part of the storage station can be heated in order to preheat those polymer moldings whose shape memory polymers are to be programmed next.

To the polymer molded parts already deformed into the temporary shape to a temperature cooling below the mold fixing temperature of the at least one polymer with shape memory and / or with thermoresponsive properties, the heat source used for the previous heating can of course be switched off in a manner known as such or the deformed polymer molded part can be brought out of reach of this heat source, in particular by means of the handling device become. However, the invention in particular also opens up the both time and energy-efficient option of cooling the polymer molded part which has already been deformed into the temporary mold, likewise by means of the fluid used to apply the deformation forces, by cooling it to a corresponding temperature below the mold fixing temperature in order to deformed polymer molded part, in particular under the constant influence of the fluid force (be it dynamic in the form of a fluid flow or jet or be it primarily static in the form of a fluid pressure difference). The fluid can be cooled very quickly, for example by means of loading with fluid or particulate coolants, for example in the form of dry ice or liquid nitrogen or the like, whereby any known cooling methods can of course also be used for cooling, at least to the mold-fixing temperature, including regionally or im Essentially bringing the polymer molded part into full contact with cooling surfaces.

• - Temperiereinrichtung des zur Erzeugung des zumindest bereichsweise auf das Polymer-Formteil einwirkenden Fluiddruckes verwendeten Fluides;
• - elektromagnetische Strahlungseinrichtung zur Bestrahlung des Polymer-Formteils mit elektromagnetischer Strahlung;
• - Induktionsheizeinrichtung; und/oder
• - Temperiereinrichtung einer das Polymer-Formteil tragenden Halteeinrichtung

umfasst. Hinsichtlich vorteilhafter konstruktiver Ausgestaltungen der Temperiereinrichtung sei auf die obigen Ausführungen verwiesen. In terms of device technology, it can therefore preferably be provided that the programming station of the device is further assigned at least one temperature control device, which in particular has at least one

• - Temperature control device of the fluid used to generate the fluid pressure acting at least in regions on the polymer molding;
• - Electromagnetic radiation device for irradiating the polymer molded part with electromagnetic radiation;
• - induction heating device; and or
• - Temperature control device of a holding device carrying the polymer molded part

includes. With regard to advantageous structural designs of the temperature control device, reference is made to the above statements.

The embodiment according to the invention also makes it possible to use suitable analytics to at least temporarily fix the shape of the at least one polymer with shape memory and / or with thermoresponsive properties of the polymer molded part converted into the temporary shape and / or its restoring behavior when the shape memory effect is triggered to quantify and monitor, where appropriate temperature, pressure, force measuring devices and the like can be used. In addition to the parameters already mentioned, e.g. Pressure or pressure difference, temperature of the fluid or fluid flow, nozzle geometry or shape of the impinging fluid flow or jet, ambient temperature, clamping force of the holding device and supplied and removed heat, process variables can also be measured and monitored to a large extent. Some exemplary examples are the optical observation of the programming process by means of cameras or the like, the monitoring of the surface temperature, in particular on the front and / or back of the polymer molded part, via infrared radiation and associated imaging methods (thermography) for verifying the temperature distribution on the surface, the measurement of the deformation force generated as a result of the fluid pressure acting on the polymer molded part or also the measurement of the force when the shape memory effect is triggered, the measurement of the change in shape both during programming and during the resetting process etc. The measured process parameters can also be via electronic feedback for an automatic control of the method according to the invention can be used.

A corresponding device therefore preferably further comprises an analytical station which, at least for, in particular quantitative, analysis of the temporary shape fixation of the at least one polymer with shape memory and / or with thermoresponsive properties of the polymer molded part converted into the temporary shape and / or its resetting behavior when triggered the shape memory effect is formed. The analytical station is arranged downstream of the programming station and, if a storage station is provided for the intermediate storage of already temporarily deformed molded polymer parts, can either be arranged upstream of this storage station or arranged downstream of it, in order to e.g. To be able to take samples for quality control.

In principle, any known - preferably, if not exclusively - thermoplastic polymers with shape memory and / or with thermoresponsive properties, such as, for example, linear block polymers, such as, for example, polyurethanes including polyurethanes with ionic or mesogenic components, block copolymers of polyethylene terephthalate and, are suitable for the process according to the invention Polyethylene oxide, block copolymers made of polystyrene and poly (1,4-butadiene), ABA triblock copolymers made of poly (2-methyl-2-oxazoline) (A block) and polytetrahydrofuran (B block), multiblock copolymers Polyurethanes with poly (ε-caprolactone) switching segments, block copolymers made of polystyrene and poly (1,4-butadiene) and the like.

Advantageous representatives of suitable polymers with shape memory and / or with thermoresponsive properties include in particular - although not exclusively - polyurethanes, preferably from the group of thermoplastic polyether urethanes and thermoplastic polyester urethanes. Examples of thermoplastic polyurethanes with shape memory and / or with thermoresponsive properties which are found to be suitable include, for example, thermoplastic polyurethane elastomers, the phase of which forms the hard segment or the network points from a diisocyanate, such as e.g. Methylene diphenyl 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 e.g. 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 diisocyanates mentioned and the polyols can be used individually or in any mixture with one another. The switching or 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 switching or soft segment e.g. an oligoester, in particular polyethylene adipate, polypropylene adipate, polybutylene adipate, polypentylene adipate or polyhexalen adipate, and other oligoesters have also been found to be useful. The oligoesters can e.g. 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, suberic acid, azelaic acid and sebacic acid, or with aromatic dicarboxylic acids such as e.g. Phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, e.g. in the form of a mixture of succinic, glutaric and adipic acids. To prepare the polyester polyols, it may be advantageous to use the corresponding dicarboxylic acid derivatives, e.g. Carboxylic diesters with 1 to 4 carbon atoms in the alcohol residue, carboxylic acid anhydrides or carboxylic acid chlorides to use. 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, if appropriate, as a mixture with one another. The polyester polyols also advantageously have molecular weights between about 400 and about 10,000 g / mol, preferably between about 600 and about 5,000 g / mol.

In addition, for example, polycarbonate-based polyurethane elastomers, ie thermoplastic polyester urethanes based on carbonic acid polyesters, are suitable as thermoplastic polyurethanes with shape memory and / or with thermo-responsive properties. Here, the diol in a thermoplastic polyurethane elastomer is preferably essentially completely or partially substituted by a polycarbonate having hydroxyl end groups, that is to say by a polycarbonate diol, which results from the reaction of a diol, in particular from the group consisting of ethylene glycol and 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, ditolyl, dixylyl, dinaphthyl carbonate, dialkyl carbonates, e.g. Diethyl, dipropyl, dibutyl, diamyl, dicyclohexyl carbonate, dioxolanones, e.g. Ethylene and propylene carbonate, hexanediol-1,6-bischlorocarbonate, phosgene or urea can be obtained.

In addition, in thermoplastic polyurethane elastomers with shape memory and / or with thermoresponsive properties that are found suitable, e.g. parts of the chain extender diol are substituted by a diamine. Examples of this include isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-1,3-propylenediamine, N, N'-dimethylethylenediamine and aromatic diamines such as e.g. 2,4-toluenediamine and 2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine and / or 2,6-toluenediamine and primary ortho-di-, tri- and / or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes , The diamines mentioned can also be used either individually or in any mixture with one another. Diamines as sole chain extenders are generally not suitable because the resulting polyureas cannot then be processed thermoplastically or have inadequate shape memory properties.

In thermoplastic polyester urethanes with shape memory and / or with thermoresponsive properties, it is also possible, for example, to build switching segment blocks, inter alia, from poly (ε-caprolactone) diols with number average molecular weights between about 1,000 and about 10,000. The switching temperature for the shape memory effect can vary depending on the weight of the switching segment ( Variation, for example, between about 50% by mass and about 90% by mass) and the molecular weight of the poly (e-caprolactone) diols, for example between about 40 ° C. and about 60 ° C., in particular between about 44 ° C. and about 55 ° C, vary. The crystallization temperatures are, for example, of the order of magnitude between approximately 20 ° C. and approximately 40 ° C., in particular between approximately 25 ° C. and approximately 30 ° C. Block copolymers which are composed of trans-polyisoprene and urethanes also show the shape memory effect, the reset temperature in this case being of the order of about 65 ° C., while the crystallization temperature depends on the chemical composition and, for example, between about 0 ° C. and about 30 ° C can be set. Furthermore, the use of carbon black as a filler additive can change the shape memory properties (including the recovery rate and the recovery temperature) of trans-polyisoprene. In addition, for example, polyadipate-based polyester urethanes are suitable for the process according to the invention, the switching temperature of their switching or soft segments being approximately 37 ° C. and the crystallization temperature being significantly below approximately 23 ° C., in particular below approximately 10 ° C. In addition, such a material has very good shape memory properties (shape fixability, shape resettability). For the polyester urethane described, it was on the one hand easy to process under the influence of fluid pressures, on the other hand, it was found that more than 75% of the tension applied for stretching is made available again when the shape is reset, i.e. during the triggering of the shape memory effect after programming.

Further examples of suitable polymers with shape memory and / or with thermoresponsive properties include elastomeric polymers, in particular from the group of polyvinyl chloride, ethylene-vinyl acetate copolymers, covalently cross-linked copolymer systems made from stearyl acrylate and esters of methacrylic acid and the like.

• 1 eine schematische Ansicht der Programmierung eines Polymer-Formteils aus Polymeren mit Formgedächtnis- und/oder mit thermoresponsiven Eigenschaften mittels auf dieses einwirkenden Fluiddruckes in Form eines Fluidstromes;
• 2 eine schematische Ansicht der Programmierung eines Polymer-Formteils aus Polymeren mit Formgedächtnis- und/oder mit thermoresponsiven Eigenschaften mittels einer an dieses angelegten Fluiddruckdifferenz;
• 3 eine schematische Ansicht der serienweisen Programmierung einer Mehrzahl an Polymer-Formteilen aus Polymeren mit Formgedächtnis- und/oder mit thermoresponsiven Eigenschaften nacheinander mittels mehrerer Halteeinrichtungen; und
• 4 eine schematische Ansicht der automatisierten Überführung der Polymer-Formteile in die bzw. aus den Halteeinrichtungen gemäß 3 mittels einer automatisierten Handhabungseinrichtung.

Further features and advantages of the invention result from the following description of exemplary embodiments with reference to the drawings. Show:

• 1 is a schematic view of the programming of a molded polymer part made of polymers with shape memory and / or with thermoresponsive properties by means of this acting fluid pressure in the form of a fluid stream;
• 2 a schematic view of the programming of a molded polymer part made of polymers with shape memory and / or with thermoresponsive properties by means of a fluid pressure difference applied to this;
• 3 a schematic view of the series programming of a plurality of polymer molded parts made of polymers with shape memory and / or with thermoresponsive properties in succession by means of several holding devices; and
• 4 a schematic view of the automated transfer of the molded polymer parts into or out of the holding devices according to 3 by means of an automated handling device.

In the 1 a process situation is shown schematically in which a polymer molded part 1 from shape memory polymers from a permanent - here: essentially planar or plate-shaped - permanent shape is converted into a dotted indicated temporary shape by programming the shape memory polymer under the action of force. For this purpose the polymer molding is 1 in a holding device designed, for example, in the manner of a holding frame 2 transferred from which it is positively and / or non-positively, but releasably carried. The holding device 2 has one or more - here: a central - recess 3 , which is used to program the polymer molding 1 necessary forming forces in the form of a fluid pressure, for example in the form of a gas pressure, in some areas on the polymer molding 1 to act so that it can be exposed to the fluid pressure in the intended forming areas.

For this purpose there is a device for loading the shape memory polymer of the polymer molding 1 provided with fluid pressure, which in the case of programming on the polymer molding 1 acting fluid pressure in the case of 1 around you with arrows 5 indicated fluid stream is, for example, a gas stream possibly loaded with particles, which by means of a corresponding nozzle 4 on the polymer molding 1 in the area of the recess 3 the holding device 2 is applied. The fluid flow 5 can in particular be tempered to the polymer molding 1 on the one hand, during programming to heat to a temperature which corresponds at least to the switching temperature of the shape memory polymer used, which can be done, for example, by means of a heating device, not shown in the drawing. In addition, the fluid flow 5 after the polymer molding 1 has been brought into its dotted, indicated temporary shape to cool the polymer molding 1 at least to the shape fixing temperature of the shape memory polymer used, for example by adding a coolant such as dry ice or the like.

In the 2 , in which identical or functionally identical components are provided with the same reference numerals and need no further explanation, is one of the 1 largely schematically corresponding process situation in which a polymer molded part 1 from shape memory polymers from a permanent - here: again essentially planar or plate-like - permanent shape is converted into a dotted indicated temporary shape by programming the shape memory polymer under the action of force. For this purpose the polymer molding is 1 also in a holding device designed, for example, in the manner of a holding frame 2 been transferred, which is essentially that of 1 corresponds and from which it is positively and / or non-positively, but releasably carried.

The situation of the 2 differs from that of 1 by the fact that it is on the occasion of the programming on the polymer molding 1 acting fluid pressure is not a fluid flow, but a more or less static fluid pressure difference, for example a gas pressure difference. Such a fluid pressure difference when programming the shape memory polymer to the polymer molding 1 to create, includes the device for loading the shape memory polymer of the polymer molding 1 with fluid pressure instead of a nozzle 4 (cf. the 1 ) one with an opening 6 provided pressure chamber 7 , the holding device 2 with the polymer molding 1 on the occasion of the programming of the shape memory polymer just before the opening 6 the pressure chamber 7 that is arranged at that of the pressure chamber 7 facing side of the means of the recess 3 the holding device 2 the pressure chamber 7 exposed area of the molded polymer part 1 the inside of the pressure chamber 7 prevailing pressure, while at the of the pressure chamber 7 opposite side of the means of the recess 3 the exposed area of the polymer molding 1 Ambient pressure is present. While in the present case inside the pressure chamber 7 an overpressure relative to ambient pressure has been set, as is the arrow 8a suggests, it is of course also possible instead to provide a negative pressure in the interior of the pressure chamber in relation to ambient pressure up to a vacuum, as is the case with the arrow 8b suggests. Also in the case of the embodiment according to the 2 can in particular the inside of the pressure chamber 7 fluid in particular be tempered to the polymer molding 1 on the one hand, during programming to heat to a temperature which corresponds at least to the switching temperature of the shape memory polymer used, which can be done, for example, by means of a heating device, not shown in the drawing. In addition, this can happen inside the pressure chamber 7 fluid located after the polymer molding 1 has been brought into its dotted, indicated temporary shape to cool the polymer molding 1 at least to the shape fixing temperature of the shape memory polymer used, for example by adding a coolant such as dry ice or the like.

The 3 shows the situation of a quasi-continuous programming of a plurality of polymer molded parts 1 from shape memory polymers one after the other, by means of a plurality of - in the present case the 1 and 2 about corresponding - holding devices 2 a programming station schematized by means of a dotted frame 10 sequentially fed and programmed there. The programming station 10 in the embodiment shown in the drawing comprises one or more of the 1 corresponding nozzle (s) 4 to act on the molded polymer parts 1 with a fluid flow 5 , but can for example also one or more pressure chambers according to the 2 include (not shown).

The holding devices 2 can in particular be connected to one another and / or to a suitable drive mechanism (likewise not shown), in order to be able to circulate them, for example. In this context, the 3 A a still empty holding device 2 recognizable, which for example on one in the 3 Storage station, not shown, for storing a plurality of polymer moldings which have not yet been programmed, that is to say are still in permanent form 1 with a polymer molding 1 is populated (cf. the 3B) , The one with the polymer molding 1 provided holding device 2 is then sent to the programming station 10 transferred and in the above with reference to the 1 programmed as described (see 3C ), whereupon the holding device 2 with the fully programmed polymer molded part converted into the temporary shape 1 transported onward (cf. the 3D ) and to a storage station 11 is transferred in which the programmed polymer molding 1 the holding device 2 can be removed and stored temporarily.

In the 4 is a schematic detailed view of the automated transfer of the molded polymer parts 1 into and out of the holding devices 2 according to 3 by means of an automated handling device 12 reproduced, which in the present case comprises a multi-axis industrial robot. The handling device 12 is positioned in such a way that it can be gripped using a suitable gripping device 13 on the one hand, the not yet programmed molded polymer parts 1 one after the other from the supply station (not shown in the drawing) into one of the interconnected holding devices 2 capable of being transferred (cf. in the 4 left), on the other hand the fully programmed polymer molded parts 1 a respective holding device 2 to remove and in particular in the storage station (see the 3 , in the 4 also not shown again) is able to transfer (cf. in the 4 right). Programming of molded polymer parts 1 happens for example in one of the 3 corresponding and in the 4 not shown again programming station, which the polymer moldings 1 by means of the holding devices 2 successively supplied and from which they also by means of the holding devices 2 be discharged in succession.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• DE 102011054925 A1 [0007]
• DE 102014104901 A1 [0007]
• DE 102015014291 A1 [0012]

Non-patent literature cited

• N. Fritzsche, T. Pretsch in Macromolecules 47, 2014, 5952-5959 [0004, 0007]
• N. Mirtschin, T. Pretsch in RSC Advances 5, 2015, 46307-46315 [0004]
• T. Pretsch, M. Ecker, M. Schildhauer, M. Maskos in J. Mater Chem. 22, 2012, 7757-7766 [0007]
• M. Ecker, T. Pretsch in RSC Advances 4, 2014, 286-292 [0007]
• M. Ecker, T. Pretsch in RSC Advances 4, 2014, 46680-46688 [0007]

Claims (17)

Process for converting molded polymer parts (1) which contain or consist entirely of at least one polymer with shape memory properties and / or with thermoresponsive properties, from a permanent shape to a temporary shape by the at least one polymer with shape memory properties and / or with thermoresponsive properties Properties are programmed under the action of force, characterized in that the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of fluid pressure acting at least in regions on the polymer molded part (1). Procedure according to Claim 1 , characterized in that the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of a fluid stream (5), in particular a gas stream, which acts on the polymer molded part (1) at least in regions. Procedure according to Claim 2 , characterized in that the fluid flow (5) is generated by means of at least one nozzle (4), with in particular at least one parameter from the group - type of fluid used for the at least partial deformation of the polymer molded part (1); - Impact angle of the fluid flow generated by the nozzle (4) on the polymer molding (1); - Impact speed of the fluid flow generated by means of the nozzle (4) on the polymer molding (1); - Distance of the nozzle (4) from the polymer molding (1); - Cross-sectional shape of the nozzle (4), such as in the form of a full jet, flat jet, cone jet or the like; - Geometry of at least one recess (3) of a holding device (1) carrying the polymer molded part (1); and - geometry of at least one recess of a template arranged between the polymer molding (1) and the nozzle (4) is adjusted according to the temporary shape of the polymer molding (1). Procedure according to Claim 2 or 3 , characterized in that the fluid stream (5) acting on the polymer molding (1) is loaded with particles. Procedure according to Claim 1 , characterized in that the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of a fluid pressure difference, in particular a gas pressure difference, applied at least in regions to the polymer molded part (1). Procedure according to Claim 5 , characterized in that the polymer molded part (1) - is arranged at an opening (6) of at least one pressure chamber (7) which is acted upon by a fluid pressure which is different from ambient pressure; or - is arranged between two mutually facing openings of two pressure chambers to which different fluid pressures are applied, with at least one parameter from the group - type of fluid used, in particular for at least regionally deforming the polymer molded part (1); - amount of fluid pressure difference; - Geometry of at least one recess (3) of a holding device (2) carrying the polymer molded part (1); and - geometry of at least one recess of a template arranged between at least one side of the polymer molded part (1) and at least one pressure chamber (7) is adjusted in accordance with the temporary shape of the polymer molded part (1). Procedure according to one of the Claims 1 to 6 , characterized in that the polymer molded part (1) is gripped at least on the occasion of the programming of the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of an, in particular automated, handling device (12), in particular - the polymer molded part (1 ) is kept in stock in its permanent form in a storage station and is transferred by means of the handling device (12) to a programming station (10), where the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of the polymer molding at least in some areas ( 1) acting fluid pressure is programmed; and / or - the polymer molded part (1) after programming in its temporary form by a programming station (10) where the at least one polymer with shape memory properties and / or with thermoresponsive properties by means of the polymer molded part (1) at least in regions fluid pressure has been programmed, is transferred to a storage station (11) in order to temporarily store the programmed polymer molding (1) in the storage station (11). Procedure according to Claim 7 , characterized in that the polymer molded part (1) is gripped by the handling device (12) and transferred to at least one holding device (2) at least on the occasion of the programming of the at least one polymer with shape memory properties and / or with thermoresponsive properties in which the at least one polymer with shape memory properties and / or with thermoresponsive properties is programmed by means of the fluid pressure acting at least in regions on the polymer molded part (1), in particular a plurality of holding devices (2) is provided, by means of which a plurality of polymer Molded parts (1) can be programmed one after the other. Procedure according to one of the Claims 1 to 8th , characterized in that the at least one polymer with shape memory properties and / or with thermoresponsive properties of the polymer molding (1) for its programming by means of the fluid pressure acting at least in regions on the polymer molding (1) - at a temperature which is lower than the switching temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties is at least partially cold worked; or - at least partially deformed at a temperature which corresponds at least to the switching temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties, after which the polymer molding (1) at least to the shape fixing temperature of the at least one polymer with shape memory properties and / or is cooled with thermoresponsive properties, the heating of the polymer molded part (1) at least to the switching temperature of the at least one polymer with shape memory properties and / or with thermoresponsive properties, in particular by means of - heating of the polymer molded part (1) to be produced at least in regions acting fluid pressure used fluids, - irradiation of the polymer molding (1) with electromagnetic radiation, - inductive heating of the polymer molding (1); - Heating of the holding device (2) carrying the polymer molding (1), and / or - Preheating of the polymer molding (1) is carried out before programming. Procedure according to one of the Claims 1 to 9 , characterized in that at least the temporary shape fixation of the at least one polymer with shape memory and / or with thermoresponsive properties of the polymer molded part (1) converted into the temporary shape and / or its restoring behavior when the shape memory effect is triggered, in particular quantitatively, is analyzed. Device for converting polymer moldings (1) which contain or consist entirely of at least one polymer with shape memory properties and / or with thermoresponsive properties, from a permanent shape to a temporary shape, in particular for carrying out a method according to one of the Claims 1 to 10 , with at least one programming station (10), which is designed for programming the at least one polymer with shape memory properties and / or with thermoresponsive properties under the action of force, characterized in that the programming station (10) has at least one device for loading the at least one polymer with shape memory properties and / or with thermoresponsive properties with fluid pressure, in particular with gas pressure. Device after Claim 11 characterized in that the device for supplying the at least one polymer with shape memory properties and / or with thermoresponsive properties with fluid pressure comprises at least one nozzle (4) for supplying the polymer molded part (1) with a fluid stream (5), in particular at least one Group parameters - type of fluid used; - Impact angle of the fluid flow generated by the nozzle (4) on the polymer molding (1); - Impact speed of the fluid flow generated by means of the nozzle (4) on the polymer molding (1); - Distance of the nozzle (4) from the polymer molding (1); - Cross-sectional shape of the nozzle (4), such as in the form of a full jet, flat jet, cone jet or the like; - Geometry of at least one recess (3) of a holding device (2) carrying the polymer molded part (1); and - Geometry of at least one recess of a template arranged between the polymer molded part (1) and the nozzle (4) is adjustable. Device after Claim 12 , characterized in that the device for supplying the at least one polymer with shape memory properties and / or with thermoresponsive properties with fluid pressure - at least one pressure chamber (7) which is provided with an opening (6) and can be acted upon with a fluid pressure which is different from ambient pressure, the polymer The molded part (1) can be positioned in front of the opening (6); or - at least two pressure chambers each provided with an opening and which can be acted upon with different fluid pressures, the polymer molded part (1) being able to be positioned between the openings arranged opposite one another, wherein in particular at least one parameter from the group - type of fluid used; - amount of fluid pressure difference; - Geometry of at least one recess (3) of a holding device (2) carrying the polymer molded part (1); and - geometry of at least one recess of a template arranged between at least one side of the polymer molded part (1) and at least one pressure chamber is adjusted in accordance with the temporary shape of the polymer molded part (1). Device according to one of the Claims 11 to 13 , characterized in that it further comprises an, in particular automated, handling device (12) for gripping the polymer molded part (1), the device further comprising in particular - a storage station for storing polymer molded parts (1) in their permanent form, from which the polymer molded parts (1) can be transferred to the programming station (10) by means of the handling device (12); and / or - a storage station (11) for the intermediate storage of polymer moldings (1) which have been converted into their temporary form and into which the polymer moldings (1) can be transferred from the programming station (10) by means of the handling device (12). Device after Claim 14 , characterized in that the further comprises at least one holding device (2) which is designed to hold the polymer molded part (1) and into or from which the polymer molded part (1) can be transferred by means of the handling device (12), wherein In particular, a plurality of holding devices (2) are provided, which can be transferred to the programming station (10) one after the other. Device according to one of the Claims 11 to 15 , characterized in that the programming station (10) is also assigned at least one temperature control device which, in particular, has at least one temperature control device for the fluid used to generate the fluid pressure acting at least in regions on the polymer molded part (1); - Electromagnetic radiation device for irradiating the polymer molded part with electromagnetic radiation; - induction heating device; and / or - temperature control device of a holding device (2) carrying the polymer molded part (1). Device according to one of the Claims 11 to 16 , characterized in that it further comprises an analysis station which, at least for, in particular quantitative, analysis of the temporary shape fixation of the at least one polymer with shape memory and / or with thermoresponsive properties of the polymer molded part (1) and / or converted into the temporary shape whose reset behavior is formed when the shape memory effect is triggered.

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